Linear Polymer Chain. · 1 Supporting Information to Precise Grafting of Macrocyclics and Dendrons...

1

Supporting Information

to

Precise Grafting of Macrocyclics and Dendrons to a

Linear Polymer Chain.

Faheem Amir,1 Md. D. Hossain,1 Zhongfan Jia, 1 and Michael J. Monteiro1,*

1. Australian Institute for Bioengineering and Nanotechnology, The University of Queensland,

Brisbane QLD 4072, Australia

*author to whom correspondence should be sent:

e-mail: [email protected]

Electronic Supplementary Material (ESI) for Polymer Chemistry.This journal is © The Royal Society of Chemistry 2016

mailto:[email protected]

2

Table of Contents1 Synthesis of Initiators and Linkers .............................................................................................................5

2 Synthesis of Polymers and Polymer Topologies ........................................................................................6

2.1 Synthesis of PSTY28-Br (6), by ATRP ...................................................................................................6

2.2 Synthesis of PSTY28-N3 (7) by Azidation with NaN3 ............................................................................7

2.3 Synthesis of (≡)2PSTY20-Br (8) by ATRP...............................................................................................7

2.4 Synthesis of (PSTY28)2-PSTY20-Br (9) by CuAAC...................................................................................8

2.5 Synthesis of (PSTY28)2-PSTY20-N3 (10) by Azidation with NaN3 ...........................................................9

2.6 Synthesis of (PSTY28)2-PSTY20-≡ (11) by CuAAC ..................................................................................9

2.7 Synthesis of ≡(HO)-PSTY28-Br (12), (12b) by ATRP ...........................................................................10

2.8 Synthesis of ≡(HO)-PSTY25-Br (12c) by ATRP ....................................................................................10

2.9 Synthesis of ≡(HO)-PSTY25-N3 (13) by Azidation with NaN3 .............................................................11

2.10 Synthesis of c-PSTY25-OH (14) ..........................................................................................................11

2.11 Synthesis of c-PSTY25-Br (15)............................................................................................................12

2.12 Synthesis of c-PSTY25-N3 (16) ...........................................................................................................13

2.13 Synthesis of c-PSTY25-≡ (17) .............................................................................................................13

2.14 Synthesis of TIPS-≡(HO)-PSTY28-Br (18), (18b) .................................................................................14

2.15 Synthesis of TIPS-≡-(OH)-PSTY28-N3 (19) by Azidation with NaN3 ....................................................14

2.16 Synthesis of TIPS-≡-(OH)-PSTY28-N3 (19b) by Azidation with NaN3 ..................................................15

2.17 Synthesis of TIPS-≡(OH-PSTY28)2-Br (20) by CuAAC ..........................................................................15

2.18 Synthesis of TIPS-≡(OH-PSTY28)2-Br (20b) by CuAAC........................................................................15

2.19 Synthesis of TIPS-≡(OH-PSTY28)2-N3 (21) by Azidation with NaN3 ....................................................16

2.20 Synthesis of TIPS-≡(OH-PSTY28)2-N3 (21b) by Azidation with NaN3 ..................................................16

2.21 Synthesis of TIPS-≡(Br-PSTY28)2-N3 (22) ............................................................................................17

2.22 Synthesis of TIPS-≡(Br-PSTY28)2-N3 (22b) ..........................................................................................17

2.23 Synthesis of TIPS-≡(N3-PSTY28)2-N3 (23) by Azidation with NaN3 .....................................................18

2.24 Synthesis of TIPS-≡(OH-PSTY28)3-Br (24) by CuAAC ..........................................................................18

2.25 Synthesis of TIPS-≡(OH-PSTY28)3-N3 (25) by Azidation with NaN3 ....................................................19

2.26 Synthesis of TIPS-≡(Br-PSTY28)3-N3 (26)............................................................................................19

2.27 Synthesis of TIPS-≡(N3-PSTY28)3-N3 (27) ...........................................................................................19

2.28 Synthesis of TIPS-≡(HO-PSTY28)3-HO-( PSTY28-OH)3-≡-TIPS (28) by CuAAC.......................................20

2.29 Synthesis of TIPS-≡(Br-PSTY28)3-Br-( PSTY28-Br)3-≡-TIPS (29) ............................................................20

2.30 Synthesis of TIPS-≡(N3-PSTY28)3-N3-(PSTY28-N3)3-≡-TIPS (30) by Azidation with NaN3 ......................21

2.31 Synthesis of tri-cyclic architecture (31) by CuAAC...........................................................................21

2.32 Synthesis of tri-dendron architecture (32) by CuAAC......................................................................22

3

2.33 Synthesis of tetra-cyclic architecture (33) by CuAAC.......................................................................23

2.34 Synthesis of tetra-dendron architecture (34) by CuAAC..................................................................23

2.35 Synthesis of hepta-cyclic architecture (35) by CuAAC .....................................................................24

2.36 Synthesis of hepta-dendron architecture (36) by CuAAC ................................................................25

2.37 Synthesis of TIPS-≡(HO-PSTY28)2-≡ (37) by CuAAC............................................................................25

2.38 Synthesis of TIPS-≡(Br-PSTY28)2-(HO-PSTY28)2-≡-TIPS (38) by CuAAC................................................26

2.39 Synthesis of TIPS-≡(N3-PSTY28)2-(HO-PSTY28)2-≡-TIPS (39) by Azidation with NaN3 ..........................26

2.40 Synthesis of TIPS-≡(Dendron-PSTY28)2-(HO-PSTY28)2-≡-TIPS (40) by CuAAC .....................................27

2.41 Synthesis of TIPS-≡(Dendron-PSTY28)2-(Br-PSTY28)2-≡-TIPS (41) .......................................................27

2.42 Synthesis of TIPS-≡(Dendron-PSTY28)2-(N3-PSTY28)2-≡-TIPS by Azidation with NaN3 (42).................28

2.43 Synthesis of TIPS-≡(Dendron-PSTY28)2-(Cyclic-PSTY28)2-≡-TIPS (43) by CuAAC .................................28

3 Characterization of initiators and linkers ................................................................................................31

4 Characterization of PSTY28-Br (6) .............................................................................................................34

5 Characterization of PSTY28-N3 (7).............................................................................................................35

6 Characterization of (≡)2PSTY20-Br (8) .......................................................................................................36

7 Characterization of (PSTY28)2-PSTY20-Br (9)..............................................................................................37

8 Characterization of (PSTY28)2-PSTY20-N3 (10)............................................................................................37

9 Characterization of (PSTY28)2-PSTY20-≡ (11) .............................................................................................38

10 Characterization of ≡(OH)-PSTY28-Br (12) ............................................................................................39

11 Characterization of ≡(OH)-PSTY28-Br (12b) ..........................................................................................40

12 Characterization of ≡(OH)-PSTY25-Br (12c) ...........................................................................................41

13 Characterization of ≡(OH)-PSTY25-N3 (13) ............................................................................................42

14 Characterization of c-PSTY25-OH (14)...................................................................................................43

15 Characterization of c-PSTY25-Br (15) ....................................................................................................44

16 Characterization of c-PSTY25-N3 (16) ....................................................................................................45

17 Characterization of c-PSTY25-≡ (17) ......................................................................................................46

18 Characterization of TIPS-≡-(HO)-PSTY28-Br (18) ...................................................................................47

19 Characterization of TIPS-≡-(OH)-PSTY28-N3 (18b) .................................................................................48

20 Characterization of TIPS-≡-(HO)-PSTY28-N3 (19)...................................................................................49

21 Characterization of TIPS-≡-(OH)-PSTY28-N3 (19b) .................................................................................50

22 Characterization of TIPS-≡(OH-PSTY28)2-Br (20) ...................................................................................51

23 Characterization of TIPS-≡(OH-PSTY28)2-Br (20b) .................................................................................52

24 Characterization of TIPS-≡(OH-PSTY28)2-N3 (21)...................................................................................53

25 Characterization of TIPS-≡(OH-PSTY28)2-N3 (21b) .................................................................................55

26 Characterization of TIPS-≡(Br-PSTY28)2-N3 (22) ....................................................................................56

27 Characterization of TIPS-≡(Br-PSTY28)2-N3 (22b) ..................................................................................57

4

28 Characterization of TIPS-≡(N3-PSTY28)2-N3 (23) ....................................................................................59

29 Characterization of TIPS-≡(HO-PSTY28)3-Br (24) ...................................................................................60

30 Characterization of TIPS-≡(HO-PSTY28)3-N3 (25)...................................................................................61

31 Characterization of TIPS-≡(Br-PSTY28)3-N3 (26) ....................................................................................63

32 Characterization of TIPS-≡(N3-PSTY28)3-N3 (27) ....................................................................................64

33 Characterization of TIPS-≡(HO-PSTY28)3-HO-(PSTY28-OH)3-≡-TIPS (28).................................................65

34 Characterization of TIPS-≡(Br-PSTY28)3-Br-(Br-PSTY28)3-≡-TIPS (29) .....................................................66

35 Characterization of TIPS-≡(N3-PSTY28)3-N3-(PSTY28-N3)3-≡-TIPS (30).....................................................67

36 Characterization of tri-cyclic architecture (31) ....................................................................................68

37 Characterization of tri_dendron architecture (32) ..............................................................................69

38 Characterization of tetra_cyclic architecture (33) ...............................................................................69

39 Characterization of tetra_dendron architecture (34)..........................................................................70

40 Characterization of hepta_cyclic architecture (35)..............................................................................70

41 Characterization of hepta_dendron architecture (36) ........................................................................70

42 Characterization of TIPS-≡(HO-PSTY28)2-≡ (37).....................................................................................71

43 Characterization of TIPS-≡(Br-PSTY28)2-(HO-PSTY28)2-≡-TIPS (38).........................................................73

44 Characterization of TIPS-≡(N3-PSTY28)2-(HO-PSTY28)2-≡-TIPS (39) ........................................................74

45 Characterization of TIPS-≡(Dendron-PSTY28)2-(HO-PSTY28)2-≡-TIPS (40) ..............................................75

46 Characterization of TIPS-≡(Dendron-PSTY28)2-(Br-PSTY28)2-≡-TIPS (41)................................................76

47 Characterization of TIPS-≡(Dendron-PSTY28)2-(N3-PSTY28)2-≡-TIPS (42) ...............................................77

48 Characterization of TIPS-≡(Dendron-PSTY28)2-(Cyclic-PSTY28)2-≡-TIPS (43) ..........................................78

5

1 Synthesis of Initiators and Linkers Initiators 1 alkyne (hydroxyl) functional initiator (Scheme S1 and Figure S1), 2 protected alkyne

(hydroxyl) functional initiator (Scheme S2 and Figure S2) and 4 dialkyne functional initiator

(Scheme S3 and Figure S4), and linker 3 dialkyne hydroxyl linker (Scheme S3 and Figure S3) and 5

methyl 3,5-bis (propargyloxyl) benzoate (Scheme S4 and Figure S5) were synthesized according to

the literature procedures reported by our group1-2.

Scheme S1: Synthetic route for the preparation of alkyne initiator (1).

Reactants and conditions: (i) Acetone, p-TsOH, RT,16h; ii) THF, NaH, propargyl bromide, -78 oC, 16 h; iii) DOWEX, Methanol, RT 16 h; iv) THF, 2-bromoisobutyryl bromide, 0 oC - RT, 16 h.

Scheme S2: Synthetic route for the preparation of protected alkyne initiator (2).

Reactants and conditions: (i) EtMgBr, THF, reflux at 76 °C, (ii) PBr3, pyridine, ether 0 ~ 25 °C (iii) NaH/ THF, -78 °C ~ 25 °C (iv) DOWEX resin in MeOH at 40 °C (v) TEA in THF at 0 °C ~ RT for 24 h.

HO

OH

OH HO

O

O O

O

O

O

OH

OH

i ii

iviii

1

O O

OH

BrO

OSi

O

OH

Si Cl +OH OH

SiBr

Si +O

OHO

SiO

SiOH

OHO

O

O

i ii iii

iv v

BrO2

6

Scheme S3: Synthetic route for the preparation of di_alkyne linker (3) and di_alkyne initiator (4).

Reactants and conditions: (i) THF, NaH, propargyl bromide, -78 oC, 16 h; ii) THF, 2-bromoisobutyryl bromide, 0 oC - RT, 16 h.

Scheme S4: Synthetic route for the preparation of di_alkyne linker (5).

Reactants and conditions: (i) Acetone, K2CO3, RT, 48 h;

2 Synthesis of Polymers and Polymer Topologies

2.1 Synthesis of PSTY28-Br (6), by ATRPStyrene (11.2 g, 1.0×10-1 mol), PMDETA (0.24 mL, 1.1×10-3 mol), CuBr2/PMDETA (6.1×10-2 g,

2.5×10-4 mol) and initiator (0.3 g, 1.5×10-3 mol) were added to a 25 mL schlenk flask equipped with

a magnetic stirrer and purged with argon for 30 min to remove oxygen. Cu(I)Br (0.16 g, 1.1×10-3

mol) was then carefully added to the solution under an argon blanket. The reaction mixture was

further degassed for 5 min and then placed into a temperature controlled oil bath at 80 °C. After 3 h,

an aliquot was taken to check the conversion. The reaction was quenched by cooling to 0 °C in ice

bath, exposed to air, and diluted with THF (ca. 3 fold to the reaction mixture volume). The copper

salts were removed by passage through an activated basic alumina column. The solution was

concentrated by rotary evaporation and the polymer was recovered by precipitation into large

volume of MeOH (20 fold excess to polymer solution) and vacuum filtered two times. The polymer

was dried under high vacuum overnight for 24 h at 25 °C; SEC (Mn = 2820, PDI = 1.10; see SEC

OH

HO

HO OH

O

Oi ii

4

O

O

O

OBr

3

i

5O O

O O

O O

HO OH

7

trace in Figure S6) (Scheme S5; Table S1). Final conversion was calculated by gravimetry of 40%;

1H NMR (Figure S7) and MALDI-ToF (Figure S8).

Scheme S5: Synthetic route for the preparation of alkyne wedge dendron (11)

Conditions: (a) Azidation: NaN3 in DMF at 25 °C, (b) Click (feed): CuBr, PMDETA in toluene by feed at 50 °C, Click (25 °C): CuBr, PMDETA in toluene at 25 °C (one pot).

2.2 Synthesis of PSTY28-N3 (7) by Azidation with NaN3

Polymer PSTY28-Br 6 (3.5 g, 1.2×10-3 mol) was dissolved in 15 mL of DMF in a 20 mL reaction

vessel equipped with a magnetic stirrer. To this solution NaN3 (1.6 g, 2.4×10-2 mol) was added and

the mixture stirred for 24 h at 25 oC. The polymer solution was directly precipitated into

MeOH/H2O (95/5, v/v) (20-fold excess to polymer solution) from DMF, recovered by vacuum

filtration and washed exhaustively with water and MeOH. The polymer was dried under high

vacuum for 24 h at 25 °C; SEC (Mn = 2900, PDI = 1.10; Figure S9) (Scheme S5; Table S1), and

was further characterized by 1H NMR (Figure S10) and MALDI-ToF (Figure S11).

2.3 Synthesis of (≡)2PSTY20-Br (8) by ATRPStyrene (9.0 g, 8.6×10-2 mol), PMDETA (0.27 mL, 1.3×10-3 mol), CuBr2/PMDETA (1.0×10-1 g,

2.6×10-4 mol) and initiator (0.6 g, 2.5×10-3 mol) were added to a 20 mL schlenk tube equipped with

a magnetic stirrer and purged with argon for 30 min to remove oxygen. Cu(I)Br (0.18 g, 1.2×10-3

mol) was then carefully added to the solution under an argon blanket. The reaction mixture was

further degassed for 5 min and then placed into a temperature controlled oil bath at 80 °C. After 2 h,

an aliquot was taken to check the conversion. The reaction was quenched by cooling to 0 °C in ice

O

O

19

O

O

27N

NN

O

O 27N

NN O

O

NNN O

O

O

19

O

O

27N

NN

O

O 27N

NN O

O

Br

6, PSTY28-Br 7, PSTY28-N3 9, (PSTY28)2-PSTY20-Br

10, (PSTY28)2-PSTY20-N311, (PSTY28)2-PSTY20-≡

OO

27Br O

O

27N3

O

O

19O

O

Br

OO

19

OO

27N

NN

O

O 27N

NN O

O

N3

Azidation

CuAAC (25 °C)

AzidationCuAAC (feed)

8, (≡)2PSTY20-Br

O

8

bath, exposed to air, and diluted with THF (ca. 3 fold to the reaction mixture volume). The copper

salts were removed by passage through an activated basic alumina column. The solution was


volume of MeOH (20 fold excess to polymer solution) and vacuum filtered two times. The polymer

was dried under high vacuum for 24 h at 25 °C; SEC (Mn = 2300, PDI = 1.09; see SEC trace in

Figure S12) (Scheme S5; Table S1). Final conversion was calculated by gravimetry 41%; 1H NMR

(Figure S13) and MALDI-ToF (Figure S14).

2.4 Synthesis of (PSTY28)2-PSTY20-Br (9) by CuAACPSTY28-N3 7 (1.2 g, 4.3×10-4 mol) and PMDETA (4.5×10-2 mL, 2.1×10-4 mol) were dissolved in 5

mL of dry toluene in a vial. In a separate vial (≡)2-PSTY20-Br 8 (0.5 g, 2.1×10-4 mol) was dissolved

in 3.0 mL of dry toluene. Cu(I)Br (3.1×10-2 g, 2.1×10-4 mol) was taken in a 20 mL schlenk tube

equipped with magnetic stirrer wrapped with Cu wire (0.25 g, 3.9×10-3 mol). After purging all these

vessels for 30 min, polymer solution 7 was transferred to the schlenk tube by applying argon

pressure using double tip needle, and the schlenk tube was placed in a temperature controlled oil

bath at 50 °C. Polymer solution 8 was feed to the schlenk flask using a syringe pump over a period

of 60 min (feed rate was set at 20 µL/min). The reaction was stopped after a additional 60 min and

diluted with THF, and the copper slats were removed by passage through an activated basic alumina

column. The solvent was removed by rotary evaporator and the polymer recovered by precipitation

in 20-fold excess of MeOH, collected by vacuum filtration and washed exhaustively with MeOH.

The polymer was dried under high vacuum for 24 h at 25 oC; SEC (Mn = 6990, PDI = 1.13; Figure

1A) and Triple Detection SEC (Mn = 8590, PDI = 1.014) (Scheme S5; Table S1). The polymer was

further characterized by 1H NMR (Figure S15) and MALDI-ToF (Figure 2A).

9

2.5 Synthesis of (PSTY28)2-PSTY20-N3 (10) by Azidation with NaN3

Polymer (PSTY28)2-PSTY20-Br 10 (1.4 g, 1.7×10-4 mol) was dissolved in 8 mL of DMF in a

reaction vessel equipped with a magnetic stirrer. To this solution NaN3 (2.3×10-1 g, 3.5×10-3 mol)

was added and the mixture stirred for 24 h at 25 oC. The polymer solution was directly precipitated

into MeOH/H2O (95/5, v/v) (20-fold excess to polymer solution) from DMF, recovered by vacuum


vacuum for 24 h at 25 °C; SEC (Mn = 7280, PDI = 1.11; Figure S16) and Triple Detection SEC (Mn

= 8680, PDI = 1.01) (Scheme S5; Table S1). The polymer was further characterized by 1H NMR

(Figure S17) and MALDI-ToF (Figure 2B).

2.6 Synthesis of (PSTY28)2-PSTY20-≡ (11) by CuAACPolymer (PSTY28)2-PSTY20-N3 10 (1.3 g, 1.6×10-4 mol) and propargyl ether (3.0×10-1 g, 3.2×10-3

mol) and PMDETA (3.3×10-2 mL, 1.6×10-4 mol) were dissolved in 6 mL of dry toluene in a vial.

CuBr (2.3×10-2 g, 1.6×10-4 mol) was added to a 10 mL schlenk flask equipped with magnetic

stirrer wrapped with Cu wire (0.25 g, 3.9×10-3 mol) and both reaction vessels were purged with

argon for 20 min. The polymer solution was then transferred to CuBr flask by applying argon

pressure using double tip needle. The flask was placed in a temperature controlled oil bath at 25 °C

for 1.5 h. The reaction was diluted with THF and passed through alumina column to remove copper

salts. Solvent was removed by rotary evaporator and precipitated in excess of MeOH and filtered.

The polymer was dried under high vacuum for 24 h at 25 oC; SEC (Mn = 7510, PDI = 1.10).

Polymer was purified by preparative SEC to remove undesired high molecular weight polymers and

residual linker. The polymer was dried under high vacuum for 24 h at 25 °C. SEC (Mn=7860,

PDI=1.03; see SEC trace in Figure S18) and Triple Detection SEC (Mn = 8640, PDI = 1.009)

(Scheme S5; Table 1). The polymer was further characterized by 1H NMR (Figure S19) and

MALDI-ToF (Figure 2C).

10

2.7 Synthesis of ≡(HO)-PSTY28-Br (12), (12b) by ATRPStyrene (12.2 g, 9.0×10-2 mol), PMDETA (0.20 mL, 9.7×10-4 mol), Cu(II)Br2/PMDETA (7.7×10-2

g, 1.9×10-4 mol) and initiator 1 (0.6 g, 1.9×10-3 mol) were added to a 10 mL schlenk flask equipped

with a magnetic stirrer and purged with argon for 30 min to remove oxygen. Cu(I)Br (0.14 g,

9.7×10-4 mol) was then carefully added to the solution under an argon blanket. The reaction mixture

was further degassed for 5 min and then placed into a temperature controlled oil bath at 80 °C. After

6 h, an aliquot was taken to check the conversion. The reaction was quenched by cooling to 0 °C in

ice bath, exposed to air, and diluted with DCM (ca. 3 fold to the reaction mixture volume). The

copper salts were removed by passage through an activated basic alumina column. The solution was


volume of MeOH (20 fold excess to polymer solution) and vacuum filtration two times. The

polymer was dried in high vacuo overnight at 25 °C, for 12 (Mn = 3220, PDI = 1.07; see SEC trace

in Figure S20). Final conversion was calculated by gravimetry 47%. The polymer was further

characterized by 1H NMR (Figure S21) and MALDI-ToF (Figure S22). Another batch of ≡(HO)-

PSTY25-Br, 12b (Mn = 3150, PDI = 1.07; SEC Figure S23; 1H NMR Figure S24 and MALDI-ToF

Figure S25) was also synthesized by following similar procedure.

2.8 Synthesis of ≡(HO)-PSTY25-Br (12c) by ATRPStyrene (8.11g, 77.86×10-3 mol), PMDETA (0.17 mL, 8.1×10-4 mol), CuBr2/PMDETA (6.4×10-2 g,

4.05×10-4 mol) and initiator (0.5 g, 1.6277×10-3 mol) were added to a 100 mL schlenk flask

equipped with a magnetic stirrer and purged with argon for 40 min to remove oxygen. Cu(I)Br (0.12

g, 8.1×10-4 mol) was then carefully added to the solution under an argon blanket. The reaction

mixture was further degassed for 5 min and then placed into a temperature controlled oil bath at 80

°C. After 4 h, an aliquot was taken to check the conversion. The reaction was quenched by cooling

to 0 °C in ice bath, exposed to air, and diluted with THF (ca. 3 fold to the reaction mixture volume).

The copper salts were removed by passage through an activated basic alumina column. The solution

was concentrated by rotary evaporation and the polymer was recovered by precipitation into large

11

volume of MeOH (20 fold excess to polymer solution) and vacuum filtration two times. The

polymer was dried in high vacuo overnight at 25 °C, SEC (Mn = 2890, PDI = 1.11; see SEC trace in

Figure S26) (Table S1). Final conversion was calculated by gravimetry 53%. The polymer was

further characterized by 1H NMR (Figure S27) and MALDI-ToF (Figure S28).

Scheme S6: Synthetic route for the preparation of cyclic alkyne (17)

Conditions: (a) Azidation: NaN3 in DMF at 25 °C, (b) Cyclization: CuBr, PMDETA in toluene by feed at 25 °C, (c) Bromination: 2-BPB, TEA in THF; 0 °C- RT. (d) Click (25 °C): CuBr, PMDETA in toluene at 25 °C (one pot).

2.9 Synthesis of ≡(HO)-PSTY25-N3 (13) by Azidation with NaN3

Polymer 12c (2.9 g, 1.0×10-3 mol) was dissolved in 15 mL of DMF in a 20 mL reaction vessel

equipped with a magnetic stirrer. To this solution NaN3 (1.6 g, 2.4×10-2 mol) was added and the

mixture stirred for 24 h at 25 oC. The polymer solution was directly precipitated into MeOH/H2O

(95/5, v/v) (20-fold excess to polymer solution) from DMF, recovered by vacuum filtration and

washed exhaustively with water and MeOH. The polymer was dried under high vacuum for 24 h at

25 °C; SEC (Mn = 2880, PDI = 1.11; Figure S29) (Table S1). The polymer was further characterized

by 1H NMR (Figure S30) and MALDI-ToF (Figure S31).

2.10 Synthesis of c-PSTY25-OH (14)Polymer 13 (2.0 g, 6.667×10-4 mol) in 80.0 ml of dry toluene and 6.97 mL of PMDETA (33.35×10-3

mol) in 80 mL of dry toluene in another flask were purged with argon for 45 min to remove oxygen.

4.78 g of CuBr (33.35×10-3 mol) was taken in a 250 mL of dry schlenk flask and maintained under

CyclizationAzidation

12c, ≡(HO)-PSTY25-Br 13, ≡(HO)-PSTY25-N3

14, cyclic-PSTY25-OH

16, cyclic-PSTY25-N3

CuAAC (25 °C one pot)

17, cyclic-PSTY25-≡

O

HO

O

OBr

27 O

HO

O

ON3

27

N NN

O

OHOO

n

N NN

O

OOO

n

BrO

N NN

O

OO

O

n

N3

O

OO

OO

N NN

O

OOO

n

NO

OO

OO

NN

Bromination

Azidation

15, cyclic-PSTY25-Br 5

12

an argon flow in the flask at the same time. A PMDETA solution was transferred to CuBr flask by

applying argon pressure using a double tip needle to prepare CuBr/PMDETA complex. After

complex formation, the polymer solution was added via syringe pump using a syringe with pre-

filled argon. The feed rate of argon was set at 1.24 mL/min. After the addition of the polymer

solution (after 65 min), the reaction mixture was further stirred for 3 h. At the end of this period (i.e.,

feed time plus an additional 3 h), toluene was evaporated by air-flow and the copper salts were

removed by passage through an activated basic alumina column by adding few drops of glacial

acetic acid. The solvent was removed by rotary evaporator and the polymer was recovered by

precipitation into MeOH (20 fold excess to polymer solution) and collected by vacuum filtration

followed by exhaustive washing with MeOH. The polymer was dried under high vacuum for 24 h at

25 °C. A small fraction of crude product was purified by preparative SEC for characterization. SEC

(Mn = 2140, PDI = 1.04; Figure S32) (Table S1), Triple Detection SEC (Mn = 2780, PDI = 1.016).

The polymer was further characterized by 1H NMR (Figure S33) and MALDI-ToF (Figure S34).

2.11 Synthesis of c-PSTY25-Br (15)c-PSTY25-OH 14 (1.6 g, 5.867×10-4 mol), TEA (1.63 mL, 11.73×10-3 mol) and 30.0 ml of dry THF

were added under an argon blanket to a dry schlenk flask that has been flushed with argon. The

reaction was then cooled on ice bath. To this stirred mixture, a solution of 2-bromopropionyl

bromide (1.23 mL, 11.73×10-3 mol) in 10 mL of dry THF was added drop wise under argon via an

air-tight syringe over 10 min. After stirring the reaction mixture for 48 h at room temperature, the

crude polymer solution was added in 300 mL of acetone and filtered to remove salt precipitate.

Solvent was removed by rotavap and precipitated into MeOH, filtered and washed three times with

MeOH. A fraction of crude product was purified by preparative SEC for characterization. The

polymer was dried for 24 h in high vacuum oven at 25 °C. SEC (Mn = 2350, PDI = 1.04; see SEC

trace in Figure S35) (Table S1). The polymer was further characterized by 1H NMR (Figure S36)

and MALDI-ToF (Figure S37).

13

2.12 Synthesis of c-PSTY25-N3 (16)Polymer c-PSTY25-Br 15 (1.5 g, 0.5×10-3 mol) was dissolved in 15 mL of DMF in a 20 mL reaction

vessel equipped with a magnetic stirrer. To this solution NaN3 (1.6 g, 2.4×10-2 mol) was added and

the mixture stirred for 24 h at 25 oC. The polymer solution was directly precipitated into



vacuum for 24 h at 25 °C; SEC (Mn = 2250, PDI = 1.04; Figure S38) (Table S1) and Triple

Detection SEC (Mn = 2930, PDI = 1.02). The polymer was further characterized by 1H NMR


2.13 Synthesis of c-PSTY25-≡ (17)Polymer c-PSTY25-N3 16 (0.4 g, 0.133×10-3 mol), PMDETA (27.87×10-3 mL, 0.133×10-3 mol) and

methyl 3,5-bis (propargyloxyl) benzoate 5 (0.49 g, 1.99×10-3 mol) were dissolved in 3.0 mL

toluene. CuBr (19.0×10-3 g, 1.33×10-4 mol) was added to a 10 mL schlenk flask equipped with

magnetic stirrer and both of the reaction vessels were purged with argon for 20 min. The polymer

solution was then transferred to CuBr flask by applying argon pressure using double tip needle. The

reaction mixture was purged with argon for a further 2 min and the flask was placed in a

temperature controlled oil bath at 25 °C for 1.5 h. The reaction was then diluted with THF (ca. 3

fold to the reaction mixture volume), and passed through activated basic alumina to remove the

copper salts. The solution was concentrated by rotary evaporator and the polymer was recovered by

precipitation into a large amount of MeOH (20 fold excess to polymer solution) and filtration. The

polymer was purified by preparative SEC to remove excess linker as well as high MW impurities.

After precipitation and filtration, the polymer was dried in vacuo for 24 h at 25 °C. SEC (Mn=2440,

PDI=1.04; see SEC trace in Figure S41) (Table 1) and Triple Detection SEC (Mn=3170, PDI=1.02).


14

2.14 Synthesis of TIPS-≡(HO)-PSTY28-Br (18), (18b) Styrene (8 g, 6.3×10-2 mol), PMDETA (1.3×10-1 mL, 6.4×10-4 mol), Cu(II)Br2/PMDETA (5.1×10-2

g, 1.29×10-4 mol) and initiator 2 (0.6 g, 1.2×10-3 mol) were added to a 20 mL schlenk flask

equipped with a magnetic stirrer and purged with argon for 30 min to remove oxygen. Cu(I)Br

(9.2×10-2 g, 6.4×10-4 mol) was then carefully added to the solution under an argon blanket. The

reaction mixture was further degassed for 5 min and then placed into a temperature controlled oil

bath at 80 °C. After 11 h an aliquot was taken to check the conversion. The reaction was quenched

by cooling the reaction mixture to 0 °C, exposure to air, and dilution with THF. The copper salts

were removed by passage through an activated basic alumina column. The solution was

concentrated by rotary evaporator and the polymer was recovered by precipitation into large volume

of MeOH (20 fold excess to polymer solution) and vacuum filtration two times. The polymer was

dried under high vacuum for 24 hr overnight at 25 °C. SEC (Mn = 3450, PDI = 1.06; see SEC trace

in Figure S44) (Table S1). Final conversion was calculated by gravimetry (48%); 1H NMR (Figure

S45) and MALDI-ToF (Figure S46). Another batch of TIPS-≡(HO)-PSTY28-Br, 18b (Mn = 3410,

PDI = 1.08; SEC Figure S47) (Table S1); 1H NMR Figure S48; MALDI-ToF Figure S49) was also

synthesized by following similar procedure.

2.15 Synthesis of TIPS-≡-(OH)-PSTY28-N3 (19) by Azidation with NaN3

Polymer TIPS-≡(OH)-PSTY28-Br 18 (1.4 g, 4.0×10-4 mol) was dissolved in 10 mL of DMF in a 20

mL reaction vessel equipped with a magnetic stirrer. To this solution NaN3 (5.2×10-1 g, 8.1×10-3

mol) was added and the mixture stirred for 24 h at 25 oC. The polymer solution was directly

precipitated into MeOH/H2O (95/5, v/v) (20-fold excess to polymer solution) from DMF, recovered

by vacuum filtration and washed exhaustively with water and MeOH. The polymer was dried under

high vacuum for 24 h at 25 °C; SEC (Mn = 3540, PDI = 1.05; Figure S50) (Table S1). The polymer

was further characterized by 1H NMR (Figure S51) and MALDI-ToF (Figure S52).

15

2.16 Synthesis of TIPS-≡-(OH)-PSTY28-N3 (19b) by Azidation with NaN3

Polymer TIPS-≡(OH)-PSTY28-Br 18b (2.9 g, 8.5×10-4 mol) was dissolved in 15 mL of DMF in a

reaction vessel equipped with a magnetic stirrer. To this solution NaN3 (1.1 g, 1.7×10-2 mol) was

added and the mixture stirred for 24 h at 25 oC. The polymer solution was directly precipitated into



vacuum for 24 h at 25 °C; SEC (Mn = 3530, PDI = 1.07; Figure S53) (Table S1). The polymer was


2.17 Synthesis of TIPS-≡(OH-PSTY28)2-Br (20) by CuAACPolymer TIPS-≡(OH)-PSTY28-N3 19 (1.1 g, 3.1×10-4 mol), ≡(OH)-PSTY28-Br 12 (1.0 g, 3.1×10-4

mol) and PMDETA (6.4×10-2 mL, 3.1×10-4 mol) were dissolved in 10 mL of dry toluene in a 20

mL vial. Cu(I)Br (4.4×10-2 g, 3.1×10-4 mol) was taken in a 20 mL schlenk tube equipped with

magnetic stirrer wrapped with Cu wire (0.25 g, 3.9×10-3 mol). Both vessels were purged with argon

for 30 min. The polymer solution was then transferred to the schlenk tube by applying argon


bath at 25 °C. The reaction was stopped after 1.5 h and diluted with THF, and the copper salts were

removed by passage through an activated basic alumina column. The solvent was removed by

rotary evaporator and the polymer recovered by precipitated in 20-fold excess of MeOH, collected

by vacuum filtration and washed exhaustively with MeOH. The polymer was dried under high

vacuum for 24 h at 25 oC; SEC (Mn = 6480, PDI = 1.08; Figure S56) (Table S1). The polymer was


2.18 Synthesis of TIPS-≡(OH-PSTY28)2-Br (20b) by CuAACPolymer TIPS-≡(OH)-PSTY28-N3 19b (2.8 g, 7.9×10-4 mol), ≡(OH)-PSTY28-Br 12b (2.49 g,

7.9×10-4 mol) and PMDETA (1.6×10-1 mL, 7.9×10-4 mol) were dissolved in 15 mL of dry toluene

in a 20 mL vial. Cu(I)Br (1.13×10-1 g, 7.9×10-4 mol) was taken in a 25 mL schlenk flask equipped

with magnetic stirrer wrapped with Cu wire (0.5 g, 7.8×10-3 mol). Both vessels were purged with

16

argon for 30 min. The polymer solution was then transferred to the schlenk tube by applying argon


bath at 25 °C. The reaction was stopped after 1.5 h and diluted with THF, and the copper salts were




vacuum for 24 h at 25 oC; SEC (Mn = 6610, PDI = 1.08; Figure S59) (Table S1). The polymer was


2.19 Synthesis of TIPS-≡(OH-PSTY28)2-N3 (21) by Azidation with NaN3

Polymer TIPS-≡(OH-PSTY28)2-Br 20 (1.9 g, 2.7×10-4 mol) was dissolved in 15 mL of DMF in a

reaction vessel equipped with a magnetic stirrer. To this solution NaN3 (3.5×10-1 g, 5.4×10-3 mol) was



filtration and washed exhaustively with water and MeOH. The polymer was dried under high vacuum

for 24 h at 25 °C; SEC (Mn = 6980, PDI = 1.08). The polymer was further purified by preparative SEC,

and reprecipitated in 10x volume MeOH, and recovered by vacuum filtration. The polymer was dried

under high vacuum for 24 h at 25 °C; SEC (Mn = 7000, PDI = 1.05; Figure S62) (Table S1). The

polymer was further characterized by 1H NMR (Figure S63) and MALDI-ToF (Figure S64).

2.20 Synthesis of TIPS-≡(OH-PSTY28)2-N3 (21b) by Azidation with NaN3

Polymer TIPS-≡(OH-PSTY28)2-Br 20b (5.2 g, 7.8×10-4 mol) was dissolved in 25 mL of DMF in a

reaction vessel equipped with a magnetic stirrer. To this solution NaN3 (1.0 g, 1.5×10-2 mol) was




17

for 24 h at 25 °C; SEC (Mn = 6660, PDI = 1.07; Figure S65) (Table S1). The polymer was further

characterized by 1H NMR (Figure S66) and MALDI-ToF (Figure S67).

2.21 Synthesis of TIPS-≡(Br-PSTY28)2-N3 (22) TIPS-≡(OH-PSTY28)2-Br 21 (0.2 g, 2.8×10-5 mmol) and TEA (1.5×10-1 mL, 1.1×10-3 mol) were

dissolved in 2 ml of dry THF in a 10 mL schlenk tube and purged for 10 min. The reaction mixture

was cooled on ice and a solution of 2-bromopropionyl bromide (1.2×10-1 mL, 1.1×10-3 mol) in 2 mL of

dry THF was transferred drop-wise to the schlenk tube by applying argon pressure using double tip

needle. The reaction mixture was further purged for 2 minutes and then stirred for 48 h at room

temperature. The polymer was precipitated into MeOH, filtered and washed exhaustively with MeOH.

The polymer was dried for 24 h under high vacuum at 25 °C. SEC (Mn = 7170, PDI = 1.07; Figure S68)

(Table S1). The polymer was further characterized by 1H NMR (Figure S69) and MALDI-ToF (Figure

S70).

2.22 Synthesis of TIPS-≡(Br-PSTY28)2-N3 (22b) TIPS-≡(OH-PSTY28)2-Br 21b (2.6 g, 3.9×10-4 mmol) and TEA (2.17 mL, 1.5×10-2 mol) were


was cooled on ice and a solution of 2-bromopropionyl bromide (1.67 mL, 1.5×10-2 mol) in 5 mL of dry

THF was transferred drop-wise to the schlenk tube by applying argon pressure using double tip needle.

The reaction mixture was further purged for 2 minutes and then stirred for 48 h at room temperature.

The polymer was precipitated into MeOH, filtered and washed exhaustively with MeOH. The polymer

was dried for 24 h under high vacuum at 25 °C. SEC (Mn = 6830, PDI = 1.06). The polymer was

further purified by preparative SEC, and reprecipitated in 10x volume MeOH, and recovered by

vacuum filtration. The polymer was dried under high vacuum for 24 h at 25 °C; SEC (Mn = 7080, PDI

= 1.04; Figure S71) (Table S1). The polymer was further characterized by 1H NMR (Figure S72) and

MALDI-ToF (Figure S73).

18

2.23 Synthesis of TIPS-≡(N3-PSTY28)2-N3 (23) by Azidation with NaN3

TIPS-≡(Br-PSTY28)2-N3 22 (0.17 g, 2.3×10-5 mol), was dissolved in 2.5 mL of DMF in a reaction

vessel equipped with magnetic stirrer. To this solution, NaN3 (9.2×10-2 g, 1.4×10-3 mol) was added and

the mixture stirred for 24 h at room temperature. The polymer solution was directly precipitated into

MeOH/H2O (95/5, v/v) (20 fold excess to polymer solution) from DMF, recovered by vacuum


for 24 h at 25 °C, SEC (Mn = 7180, PDI = 1.05). The polymer was further purified by preparative SEC,


under high vacuum for 24 h at 25 °C; SEC (Mn = 7160, PDI = 1.03; Figure 3A) (Table S1). The


2.24 Synthesis of TIPS-≡(OH-PSTY28)3-Br (24) by CuAACPolymer TIPS-≡(OH-PSTY28)2-N3 21 (7.3×10-1 g, 1.0×10-4 mol) and ≡(OH)-PSTY28-Br 12 (3.5×10-

1 g, 1.0×10-4 mol) and PMDETA (2.2×10-2 mL, 1.0×10-4 mol) were dissolved in 8 mL of dry

toluene in a 20 mL vial. Cu(I)Br (1.5×10-2 g, 1.0×10-4 mol) was taken in a 20 mL schlenk tube

equipped with magnetic stirrer wrapped with Cu wire (0.25 g, 3.9×10-3 mol). Both vessels were

purged with argon for 30 min. The polymer solution was then transferred to the schlenk tube by

applying argon pressure using double tip needle, and the tube was placed in a temperature

controlled oil bath at 25 °C. The reaction was stopped after 1.5 h and diluted with THF, and the

copper salts were removed by passage through an activated basic alumina column. The solvent was

removed by rotary evaporator and the polymer recovered by precipitated in 20-fold excess of

MeOH, collected by vacuum filtration and washed exhaustively with MeOH. The polymer was

dried under high vacuum for 24 h at 25 oC; SEC (Mn = 9050, PDI = 1.10; Figure S76) (Table S1).


19

2.25 Synthesis of TIPS-≡(OH-PSTY28)3-N3 (25) by Azidation with NaN3

Polymer TIPS-≡(OH-PSTY25)3-Br 24 (9.5×10-1 g, 9.2×10-5 mol) was dissolved in 10 mL of DMF in a

reaction vessel equipped with a magnetic stirrer. To this solution NaN3 (1.2×10-1 g, 1.8×10-3 mol) was




for 24 h at 25 °C; SEC (Mn = 8610, PDI = 1.16). The polymer was further purified by preparative SEC,


under high vacuum for 24 h at 25 °C; SEC (Mn = 10670, PDI = 1.04; Figure S79) (Table S1). The


2.26 Synthesis of TIPS-≡(Br-PSTY28)3-N3 (26)TIPS-≡(OH-PSTY28)3-N3 25 (0.19×10-1 g, 1.8×10-5 mmol), TEA (1.5×10-1 mL, 1.0×10-3 mol) were


was cooled on ice and a solution of 2-bromopropionyl bromide (1.1×10-1 mL, 1.0×10-3 mol) in 2 mL of

dry THF was transferred drop-wise to the schlenk tube by applying argon pressure using double tip

needle. The reaction mixture was further purged for 2 minutes and then stirred for 48 h at room

temperature. The polymer was precipitated into MeOH, filtered and washed exhaustively with MeOH.

The polymer was dried for 24 h under high vacuum at 25 °C. SEC (Mn = 9090, PDI = 1.12; Figure S82)


S84).

2.27 Synthesis of TIPS-≡(N3-PSTY28)3-N3 (27)TIPS-≡(Br-PSTY28)3-N3 26 (1.6×10-1 g, 1.4×10-5 mol), was dissolved in 3 mL of DMF in a reaction

vessel equipped with a magnetic stirrer. To this solution NaN3 (8.6×10-2 g, 1.3×10-3 mol) was added

and the mixture stirred for 24 h at 25 oC. The polymer solution was directly precipitated into


filtration and washed exhaustively with water MeOH. The polymer was dried under high vacuum for

20

24 h at 25 °C; SEC (Mn = 8970, PDI= 1.16). The polymer was further purified by preparative SEC,


under high vacuum for 24 h at 25 °C; SEC (Mn = 10830, PDI = 1.03; Figure 3B) (Table S1). The


2.28 Synthesis of TIPS-≡(HO-PSTY28)3-HO-( PSTY28-OH)3-≡-TIPS (28) by CuAACPolymer TIPS-≡(OH-PSTY28)3-N3 25 (2.8×10-1 g, 2.6×10-5 mol), 2,2-

bis(propargyloxymethyl)propan-1-ol (2.5×10-3 g, 1.3×10-5 mol) and PMDETA (1.0×10-2 mL,

5.2×10-5 mol) were dissolved in 3 mL of dry toluene in a 7 mL vial. Cu(I)Br (7.5×10-3 g, 5.2×10-5

mol) was taken in a 10 mL schlenk tube equipped with magnetic stirrer wrapped with Cu wire (0.1

g, 1.5×10-3 mol). Both vessels were purged with argon for 20 min. The polymer solution was then

transferred to the schlenk tube by applying argon pressure using double tip needle, and the tube was

placed in a temperature controlled oil bath at 25 °C. The reaction was stopped after 1.5 h and

diluted with THF, and the copper salts were removed by passage through an activated basic alumina

column. The solvent was removed by rotary evaporator and the polymer recovered by precipitated

in 20-fold excess of MeOH, collected by vacuum filtration and washed exhaustively with MeOH.

The polymer was dried under high vacuum for 24 h at 25 oC; SEC (Mn = 15450, PDI = 1.20; S87)

(Table S1). The polymer was further characterized by 1H NMR (Figure S88) and MALDI-ToF

(Figure S89).

2.29 Synthesis of TIPS-≡(Br-PSTY28)3-Br-( PSTY28-Br)3-≡-TIPS (29) TIPS-≡(HO-PSTY28)3-HO-(PSTY28-OH)3-≡-TIPS 28 (2.4×10-1 g, 1.1×10-5 mmol), TEA (2.2×10-1 mL,

1.6×10-3 mol) were dissolved in 2 ml of dry THF in a 10 mL schlenk tube and purged for 10 min. The

reaction mixture was cooled on ice and a solution of 2-bromopropionyl bromide (1.7×10-1 mL, 4.2×10-

3 mol) in 2 mL of dry THF was transferred drop-wise to the schlenk tube by applying argon pressure

using double tip needle. The reaction mixture was further purged for 2 minutes and then stirred for 48

h at room temperature. The polymer was precipitated into MeOH, filtered and washed exhaustively

with MeOH. The polymer was dried for 24 h under high vacuum at 25 °C. SEC (Mn = 17000, PDI =

21

1.12; see SEC trace in Figure S90) (Table S1). The polymer was further characterized by 1H NMR


2.30 Synthesis of TIPS-≡(N3-PSTY28)3-N3-(PSTY28-N3)3-≡-TIPS (30) by Azidation with NaN3

TIPS-≡(Br-PSTY28)3-Br-(PSTY28-Br)3-≡-TIPS 29 (2.0×10-1 g, 9.4×10-6 mol), was dissolved in 2.5 mL

of DMF in a reaction vessel equipped with a magnetic stirrer. To this solution NaN3 (1.2×10-1 g,

1.9×10-3 mol) was added and the mixture stirred for 24 h at 25 oC. The polymer solution was directly

precipitated into MeOH/H2O (95/5, v/v) (20-fold excess to polymer solution) from DMF, recovered by

vacuum filtration and washed exhaustively with water and MeOH. The polymer was dried under high

vacuum for 24 h at 25 °C; SEC (Mn = 16810, PDI = 1.12). The polymer was further purified by

preparative SEC, and reprecipitated in 10x volume MeOH, and recovered by vacuum filtration. The

polymer was dried under high vacuum for 24 h at 25 °C; SEC (Mn = 21720, PDI = 1.04; Figure 3C)


S94).

2.31 Synthesis of tri-cyclic architecture (31) by CuAACPolymer TIPS-≡(N3-PSTY28)2-N3 23 (3.1×10-2 g, 4.3×10-6 mol), polymer c-PSTY25-≡ 17 (4.2×10-2

g, 1.7×10-5 mol) and PMDETA (2.7×10-3 mL, 1.2×10-5 mol) were dissolved in 0.8 mL of dry




applying argon pressure using a double tip needle, and the tube was placed in a temperature

controlled oil bath at 50 °C. The reaction was stopped after 1 h and diluted with THF, and the


removed by rotary evaporator and the polymer recovered by precipitation in 20-fold excess of


dried under high vacuum for 24 h at 25 oC; SEC (Mn = 13620, PDI = 1.13). The polymer was

22

purified by preparative SEC to remove undesired high molecular weight polymer and residual

reactant polymers. The polymer was reprecipitated in 10x volume MeOH, and recovered by

vacuum filtration. The polymer was dried under high vacuum for 24 h at 25 °C. SEC (Mn = 12620,

PDI = 1.04; Figure 4A), Triple detection (Mn = 16990, PDI = 1.01) (Table 1) and 1H NMR (Figure

S95).

2.32 Synthesis of tri-dendron architecture (32) by CuAACPolymer TIPS-≡(N3-PSTY28)2-N3 23 (1.6×10-2 g, 2.2×10-6 mol), polymer (PSTY28)2-PSTY20-≡ 11

(7.0×10-2 g, 8.9×10-6 mol) and PMDETA (1.3×10-3 mL, 6.7×10-6 mol) were dissolved in 0.8 mL of

dry toluene in a 4 mL vial. Cu(I)Br (9.6×10-4 g, 6.7×10-6 mol) was taken in a 10 mL schlenk tube












PDI = 1.07; Figure 4B), Triple detection (Mn = 33400, PDI = 1.01) (Table 1) and 1H NMR (Figure

S96).

23

2.33 Synthesis of tetra-cyclic architecture (33) by CuAACPolymer TIPS-≡(N3-PSTY28)3-N3 27 (3.2×10-2 g, 2.9×10-6 mol), polymer c-PSTY25-≡ 17 (3.6×10-2

g, 1.4×10-5 mol) and PMDETA (2.4×10-3 mL, 1.1×10-5 mol) were dissolved in 0.8 mL of dry













PDI = 1.05; Figure 4C), Triple detection (Mn = 25240, PDI = 1.02) (Table 1) and 1H NMR (Figure

S97).

2.34 Synthesis of tetra-dendron architecture (34) by CuAACPolymer TIPS-≡(N3-PSTY28)3-N3 27 (1.8×10-2 g, 1.6×10-6 mol), polymer (PSTY28)2-PSTY20-≡ 11

(6.5×10-2 g, 8.3×10-6 mol) and PMDETA (1.3×10-3 mL, 6.6×10-6 mol) were dissolved in 0.8 mL of

dry toluene in a 4 mL vial. Cu(I)Br (9.5×10-4 g, 6.6×10-6 mol) was taken in a 10 mL schlenk tube






24







PDI = 1.08; Figure 4D), Triple detection (Mn = 45240, PDI = 1.01) (Table 1) and 1H NMR (Figure

S98).

2.35 Synthesis of hepta-cyclic architecture (35) by CuAACPolymer TIPS-≡(N3-PSTY28)3-N3-(PSTY28-N3)3-≡-TIPS 30 (4.2×10-2 g, 1.9×10-6 mol), polymer c-

PSTY25-≡ 17 (3.7×10-2 g, 1.5×10-5 mol) and PMDETA (2.8×10-3 mL, 1.3×10-5 mol) were dissolved

in 0.8 mL of dry toluene in a 4 mL vial. Cu(I)Br (1.9×10-3 g, 1.3×10-5 mol) was taken in a 10 mL

schlenk tube equipped with magnetic stirrer wrapped with Cu wire (0.1 g, 1.5×10-3 mol). Both

vessels were purged with argon for 15 min. The polymer solution was then transferred to the

schlenk tube by applying argon pressure using a double tip needle, and the tube was placed in a

temperature controlled oil bath at 50 °C. The reaction was stopped after 1 h and diluted with THF,

and the copper salts were removed by passage through an activated basic alumina column. The

solvent was removed by rotary evaporator and the polymer recovered by precipitation in 20-fold

excess of MeOH, collected by vacuum filtration and washed exhaustively with MeOH. The

polymer was dried under high vacuum for 24 h at 25 oC; SEC (Mn = 36630, PDI = 1.17). The

polymer was purified by preparative SEC to remove undesired high molecular weight polymer and

residual reactant polymers. The polymer was reprecipitated in 10x volume MeOH, and recovered

by vacuum filtration. The polymer was dried under high vacuum for 24 h at 25 °C. SEC (Mn =

33610, PDI = 1.06; Figure 4E), Triple detection (Mn = 42940, PDI = 1.01) (Table 1) and 1H NMR

(Figure S99).

25

2.36 Synthesis of hepta-dendron architecture (36) by CuAACPolymer TIPS-≡(N3-PSTY28)3-N3-(PSTY28-N3)3-≡-TIPS 30 (2.1×10-2 g, 9.6×10-7 mol), polymer

(PSTY28)2-PSTY20-≡ 11 (6.0×10-2 g, 7.7×10-6 mol) and PMDETA (1.4×10-3 mL, 6.7×10-6 mol)

were dissolved in 0.8 mL of dry toluene in a 4 mL vial. Cu(I)Br (9.7×10-4 g, 9.9×10-6 mol) was

taken in a 10 mL schlenk tube equipped with magnetic stirrer wrapped with Cu wire (0.1 g, 1.5×10-

3 mol). Both vessels were purged with argon for 15 min. The polymer solution was then transferred

to the schlenk tube by applying argon pressure using a double tip needle, and the tube was placed in

a temperature controlled oil bath at 50 °C. The reaction was stopped after 1 h and diluted with THF,








70950, PDI = 1.12; Figure 4E), Triple detection (Mn = 83100, PDI = 1.01) (Table 1) and 1H NMR

(Figure S100).

2.37 Synthesis of TIPS-≡(HO-PSTY28)2-≡ (37) by CuAACPolymer TIPS-≡(OH-PSTY28)2-N3 21b (2.5 g, 3.7×10-4 mol) and propargyl ether (7.0×10-1 g,


in a 20 mL vial. Cu(I)Br (5.3×10-2 g, 3.7×10-4 mol) was taken in a 20 mL schlenk tube equipped



pressure using a double tip needle, and the tube was placed in a temperature controlled oil bath at

25 °C. The reaction was stopped after 1.5 h and diluted with THF, and the copper salts were


26



vacuum for 24 h at 25 oC; SEC (Mn = 6700, PDI = 1.08). The polymer was purified by preparative

SEC and recovered by precipitation. The polymer was dried under high vacuum for 24 h at 25 °C.

SEC (Mn = 6820, PDI = 1.07; Figure S101) (Table S1). The polymer was further characterized by

1H NMR (Figure S102) and MALDI-ToF (Figure S103).

2.38 Synthesis of TIPS-≡(Br-PSTY28)2-(HO-PSTY28)2-≡-TIPS (38) by CuAACPolymer TIPS-≡(Br-PSTY28)2-N3 22b (1.6 g, 2.3×10-4 mol), TIPS-≡(HO-PSTY28)2-≡ 37 (1.6 g,


in a 20 mL vial. Cu(I)Br (3.3×10-2 g, 2.3×10-4 mol) was taken in a 20 mL schlenk tube equipped



pressure using a double tip needle, and the tube was placed in a temperature controlled oil bath at

25 °C. The reaction was stopped after 1.5 h and diluted with THF, and the copper salts were




vacuum for 24 h at 25 oC; SEC (Mn = 12770, PDI = 1.18; Figure S104) (Table S1). The polymer

was further characterized by 1H NMR (Figure S105) and MALDI-ToF (Figure 5A).

2.39 Synthesis of TIPS-≡(N3-PSTY28)2-(HO-PSTY28)2-≡-TIPS (39) by Azidation with NaN3

TIPS-≡(Br-PSTY28)2-(HO-PSTY28)2-≡-TIPS 38 (3.1 g, 2.2×10-4 mol), was dissolved in 20 mL of DMF

in a reaction vessel equipped with a magnetic stirrer. To this solution NaN3 (5.7×10-1 g, 8.9×10-3 mol)

was added and the mixture stirred for 24 h at 25 oC. The polymer solution was directly precipitated

into MeOH/H2O (95/5, v/v) (20-fold excess to polymer solution) from DMF, recovered by vacuum


27

for 24 h at 25 °C; SEC (Mn = 12630, PDI = 1.13). The polymer was further purified by preparative

SEC, and reprecipitated in 10x volume MeOH, and recovered by vacuum filtration. The polymer was

dried under high vacuum for 24 h at 25 °C; SEC (Mn = 13320, PDI = 1.05; Figure S106) (Table S1).

The polymer was further characterized by 1H NMR (Figure S107) and MALDI-ToF (Figure 5B).

2.40 Synthesis of TIPS-≡(Dendron-PSTY28)2-(HO-PSTY28)2-≡-TIPS (40) by CuAACPolymer TIPS-≡(N3-PSTY28)2-(HO-PSTY28)2-≡-TIPS 39 (1.4×10-1 g, 6.4×10-6 mol), polymer

(PSTY28)2-PSTY20-≡ 11 (1.5×10-1 g, 1.9×10-5 mol) and PMDETA (2.6×10-3 mL, 1.2×10-5 mol)

were dissolved in 3 mL of dry toluene in a 7 mL vial. Cu(I)Br (1.8×10-3 g, 2.6×10-3 mol) was taken

in a 10 mL schlenk tube equipped with magnetic stirrer wrapped with Cu wire (0.25 g, 3.9×10-3

mol). Both vessels were purged with argon for 30 min. The polymer solution was then transferred to

the schlenk tube by applying argon pressure using a double tip needle, and the tube was placed in a





polymer was dried under high vacuum for 24 h at 25 oC; SEC (Mn = 21320, PDI = 1.29; Figure

S108) (Table S1), 1H NMR (Figure S109).

2.41 Synthesis of TIPS-≡(Dendron-PSTY28)2-(Br-PSTY28)2-≡-TIPS (41) TIPS-≡(Dendron-PSTY28)2-(HO-PSTY28)2-≡-TIPS 40 (2.3×10-1 g, 8.1×10-6 mmol), TEA (4.5×10-2 mL,

3.2×10-4 mol) were dissolved in 2 ml of dry THF in a 10 mL schlenk tube and purged for 10 min. The

reaction mixture was cooled on ice and a solution of 2-bromopropionyl bromide (3.5×10-2 mL, 4.2×10-

3 mol) in 2 mL of dry THF was transferred drop-wise to the schlenk tube by applying argon pressure

using double tip needle. The reaction mixture was further purged for 2 minutes and then stirred for 48

h at room temperature. The polymer was precipitated into MeOH, filtered and washed exhaustively

28

with MeOH. The polymer was dried for 24 h under high vacuum at 25 °C. SEC (Mn = 22880, PDI =

1.23; Figure S110) (Table S1), 1H NMR (Figure S111).

2.42 Synthesis of TIPS-≡(Dendron-PSTY28)2-(N3-PSTY28)2-≡-TIPS by Azidation with NaN3 (42)

TIPS-≡(Dendron-PSTY28)2-(Br-PSTY28)2-≡-TIPS 41 (1.9×10-1 g, 6.7×10-6 mol), was dissolved in 2.5

mL of DMF in a reaction vessel equipped with a magnetic stirrer. To this solution NaN3 (2.6×10-2 g,

4.0×10-4 mol) was added and the mixture stirred for 24 h at 25 oC. The polymer solution was directly

precipitated into MeOH/H2O (95/5, v/v) (20-fold excess to polymer solution) from DMF, recovered by

vacuum filtration and washed exhaustively with water and MeOH. The polymer was dried under high

vacuum for 24 h at 25 °C; SEC (Mn = 21580, PDI = 1.26). The polymer was further purified by

preparative SEC, and reprecipitated in 10x volume MeOH, and recovered by vacuum filtration. The

polymer was dried under high vacuum for 24 h at 25 °C; SEC (Mn = 27690, PDI = 1.08; Figure 6A),

Triple detection (Mn = 31950, PDI = 1.01) (Table 1), 1H NMR (Figure S114).

2.43 Synthesis of TIPS-≡(Dendron-PSTY28)2-(Cyclic-PSTY28)2-≡-TIPS (43) by CuAACPolymer TIPS-≡(Dendron-PSTY28)2-(N3-PSTY28)2-≡-TIPS 42 (7.0×10-2 g, 2.4×10-6 mol), polymer

c-PSTY25-≡ 17 (1.7×10-2 g, 7.2×10-6 mol) and PMDETA (1.0×10-3 mL, 4.8×10-6 mol) were

dissolved in 0.8 mL of dry toluene in a 4 mL vial. Cu(I)Br (6.9×10-4 g, 4.8×10-6 mol) was taken in a

10 mL schlenk tube equipped with magnetic stirrer wrapped with Cu wire (0.1 g, 1.5×10-3 mol).

Both vessels were purged with argon for 15 min. The polymer solution was then transferred to the

schlenk tube by applying argon pressure using a double tip needle, and the tube was placed in a







29



31170, PDI = 1.08; Figure 6B), Triple detection (Mn = 38520, PDI = 1.01) and 1H NMR (Figure

S115) (Table 1).

30

Table S1: Purity, Coupling efficiency, Molecular Weight Data (RI and Triple Detection) and change in Hydrodynamic Volume for all starting building blocks and products

aThe molecular weight distribution from SEC (RI detector) was based on a PSTY calibration curve. bCuAAC coupling efficiency was determined from the RI SEC traces, and calculated as follows: purity (LND)/max. purity by theory ×100. cThe molecular weight distribution determined from DMAc Triple Detection SEC with 0.03 wt % of LiCl as eluent. dPDI values from triple detection underestimate the true PDI values since light scattering is less sensitive to the low molecular weight part of the distribution. e(Mn,RI/Mn,TD).

Polymer RI detectiona Purity by LNDCouplingefficiency (%)b LND

Mn by NMR

Triple detectionc (Mn,RI/Mn,TD)e

Mn Mp PDI Mn Mp PDId

6 2820 2950 1.10 31107 2900 3050 1.10 31108 2300 2410 1.09 24309 6990 7850 1.13 88 90 8750 8590 8690 1.01410 7280 8000 1.11 88 8760 8680 8750 1.0111_crude 7510 8140 1.10 8811_prep 7860 8080 1.03 98 8850 8640 8980 1.009 0.8912 3220 3290 1.07 325012b 3150 3250 1.09 325012c 2890 2900 1.11 312013 2880 2900 1.11 298014_crude 2550 2200 1.57 8414_prep 2140 2180 1.04 99 2980 2780 2860 1.01615 2350 2400 1.04 311016 2250 2300 1.04 3180 2930 3090 1.01817 2440 2470 1.04 3520 3170 3320 1.021 0.7718 3450 3570 1.06 346018b 3410 3550 1.08 346019 3540 3630 1.05 347019b 3530 3660 1.07 347020 6480 6950 1.08 93 93 703020b 6610 6860 1.08 92 9321_crude 6980 6990 1.08 9221_prep 7000 7110 1.05 98 702021b_ crude 6660 6940 1.07 9222 7170 7210 1.07 732022b_ crude 6830 7090 1.06 9222b _prep 7080 7220 1.04 99.5 722023_ crude 7180 7210 1.05 9523_prep 7160 7270 1.03 99 735024 9050 10260 1.10 87 1046025_ crude 8610 10470 1.16 8425_prep 10670 10770 1.04 9826 9090 10750 1.12 86 1091027_ crude 8970 10730 1.16 8527_prep 10830 10980 1.03 98 1093028 15450 20620 1.20 75 75 2110029 17000 21180 1.12 77 2218030_crude 16810 21150 1.12 7530_prep 21720 21990 1.04 98 2217037_crude 6700 6900 1.08 9237_prep 6820 7020 1.07 99.5 688038_crude 12770 13900 1.18 85 1669039_crude 12630 13950 1.13 8039_prep 13320 13750 1.05 97 1560040_crude 21320 28240 1.29 81 92 3216041_crude 22880 28170 1.23 81 32670

31

3 Characterization of initiators and linkers

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

3.000

6.099

0.943

4.004

4.008

(a)

(b)

OO

OBr

HO

a bc d

e

f

b,dc

fe

a

OO

OBr

HO

i

dc

fj

he

g

a

bi

ab c

d

ef

gj

k

hk

Figure S1: (a) 1H NMR (400 MHz) and (b) 13C NMR (100 MHz) of 1, recorded in CDCl3 at 298K

170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 ppm

OSi

O

OH

BrO

OSi

O

OH

BrO

ab c

d

ef

g

h

c,g d, e h a,b f

ab

c d e

f

g

hi

j kl

m

k d cf

jh

e

l

g

m a b

i

(a)

(b)

1.01.52.02.53.03.54.04.55.05.5 ppm

3.146

21.198

6.000

4.026

4.026

Figure S2: (a) 1H NMR (400 MHz) and (b) 13C NMR (100 MHz) of 2 recorded in CDCl3 at 298K

32

85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 ppm

5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

3.000

1.921

4.006

2.001

4.014

OHO

O

OHO

O

a bc d

eb

e

d

c

f

e

a

b

(a)

(b)

a

ab c

de

f

g

g

c d


OO

OBr

O

OO

OBr

O

2030405060708090100110120130140150160170 ppm

5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5 ppm

3.000

6.072

1.810

4.033

6.076

a bc d

e

f

b,dc

fe

h

d c

f

jh

eg

a

b

i

(a)

(b)

a

ab c

de

f

gj

i


33

2030405060708090100110120130140150160170 ppm

O O

O O

O O

O O

1.52.02.53.03.54.04.55.05.56.06.57.07.5 ppm

2.000

3.040

4.086

1.044

2.035

a

b

c

d

e

d

b

c

e

h

d

cf

h

eg

a

b

i

(a)

(b)

a

ab c d

e

f g

i


34

4 Characterization of PSTY28-Br (6)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2 2.5 3 3.5 4 4.5 5

w (M

)

Log MW

(a) PSTY-Br (6)

LND simulation

Figure S6: SEC-RI trace of PSTY28-Br (6) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.5 ppm

9.000

84.144

2.010

0.987

O

O

27

Br a, c

f

c

b

ab

d e f

d, e

PSTY28-Br, 6

Figure S7: 1H 1D DOSY NMR spectrum of PSTY28-Br (6) recorded in CDCl3 at 298K (500 MHz).

3136.423

0

500

1000

1500

Inte

ns. [

a.u.

]

2000 3000 4000m/z

3136.423

0

500

1000

1500

Inte

ns. [

a.u.

]

3000 3050 3100 3150 3200 3250m/z

Expt.= 3136.423, cal. [M+Ag+] = 3136.73

O

O

27

M

Figure S8: Full and expanded MALDI-ToF mass spectra of PSTY28-Br (6) acquired in reflectron mode with Ag salt as cationizing agent and DCTB matrix.

35

5 Characterization of PSTY28-N3 (7)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2 2.5 3 3.5 4 4.5 5

w (M

)

Log MW

(a) PSTY-N3 (7)

LND simulation

Figure S9: SEC-RI trace of PSTY28-N3 (7) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.5 ppm

9.000

84.046

1.980

0.977

O

O

27

N3

a, c

f

c

b

ab

d e f

d, e

Figure S10: 1H 1D DOSY NMR spectrum of PSTY28-N3 (7) recorded in CDCl3 at 298K (500 MHz).

3152.867

0

500

1000

1500

Inte

ns. [

a.u.

]

2000 3000 4000m/z

3152.867

0

500

1000

1500

Inte

ns. [

a.u.

]

3050 3100 3150 3200 3250m/z

Expt.= 3152.867, cal. [M-N2+Ag+] = 3151.74

O

O

27

N3

M

Figure S11: Full and expanded MALDI-ToF mass spectra of PSTY28-N3 (7) acquired in reflectron mode with Ag salt as cationizing agent and DCTB matrix.

36

6 Characterization of (≡)2PSTY20-Br (8)

0

0.0001

0.0002

0.0003

0.0004

0.0005

0.0006

2 2.5 3 3.5 4 4.5 5

w (M

)

Log MW

(b) (≡)2-PSTY-Br (22)

LND simulation

Figure S12: SEC-RI trace of (≡)2PSTY20-Br (8) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm

9.072

62.057

6.000

4.084

0.972

O

O

19O

O

Br

f ,e

i

a

c

d

ba b

c d

e

fg h i

g, h

Figure S13: 1H 1D DOSY NMR spectrum of (≡)2PSTY20-Br (8) recorded in CDCl3 at 298K (500 MHz).

2455.016

0.00

0.25

0.50

0.75

1.00

1.25

4x10

Inte

ns. [

a.u.

]

1500 2000 2500 3000 3500m/z

2455.016

0.00

0.25

0.50

0.75

1.00

1.25

4x10

Inte

ns. [

a.u.

]

2350 2400 2450 2500 2550m/z

Expt.= 2455.016, cal. [M+Ag+] = 2454.30

O

O

19O

O

Expt.= 2473.355, cal. [M+Na+] = 2474.50

M

Figure S14: Full and expanded MALDI-ToF mass spectra of (≡)2PSTY20-Br (8) acquired in reflectron mode with Ag salt as cationizing agent and DCTB matrix.

37

7 Characterization of (PSTY28)2-PSTY20-Br (9)

1.01.52.02.53.03.54.04.55.0 ppm

27.742

230.748

10.000

4.981

1.977

O

O

19

O

O

27

N

NN

O

O 27N

NN O

O

Br

bc

f g

h

j

ki

a

n

fg, n

b, h, i

d, e, l ,ma, c, j, k

ed

l m DMF

Figure S15: 1H 1D DOSY NMR spectrum of (PSTY28)2-PSTY20-Br (9) recorded in CDCl3 at 298K (500 MHz).

8 Characterization of (PSTY28)2-PSTY20-N3 (10)

0

0.0001

0.0002

0.0003

0.0004

0.0005

0.0006

2.5 3 3.5 4 4.5 5

w (M

)

Log MW

(a) PSTY-N3 (7)

(b) (≡)2-PSTY-Br (8)

(c) (PSTY)2-PSTY-N3 (10)

LND simulation

Figure S16: SEC-RI trace of (PSTY28)2-PSTY20-N3 (10) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm

27.422

231.283

10.000

0.981

4.008

1.981

O

O

19

O

O

27

N

NN

O

O 27N

NN O

O

N3

bc

f g

h

j

ki

a

n

fg

b, h, i

d, e, l ,m a, c, j, k

ed

l m

n

DMF

Figure S17: 1H 1D DOSY NMR spectrum of (PSTY28)2-PSTY20-N3 (10) recorded in CDCl3 at 298K (500 MHz).

38

9 Characterization of (PSTY28)2-PSTY20-≡ (11)

Figure S18: SEC-RI trace of (PSTY28)2-PSTY20-≡ (11) crude (a) and purified (b) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm

27.820

231.069

10.000

7.927

2.926

O

O

19

O

O

27

N

NN

O

O 27N

NN O

O

N

NN O

bc

f g

h

j

ki

a

o

f, ng, o, p

b, h, i

d, e, l, m, q a, c, j, k

ed

l mp

n

q

q

Figure S19: 1H 1D DOSY NMR spectrum of (PSTY28)2-PSTY20-≡ (11) recorded in CDCl3 at 298K (500 MHz).

0

0.0001

0.0002

0.0003

0.0004

0.0005

0.0006

2.5 3 3.5 4 4.5 5

w (M

)

Log MW

(a) PSTY-N3 (7)

(b) (≡)2-PSTY-Br (8)

(c) (PSTY)2-PSTY-≡ (11)

LND simulation

(A)

0

0.0001

0.0002

0.0003

0.0004

0.0005

0.0006

2.5 3 3.5 4 4.5 5

w (M

)

Log MW

(a) PSTY-N3 (7)

(b) (≡)2-PSTY-Br (8)

(c) (PSTY)2-PSTY-≡ (11)

LND simulation

(B)

39

10 Characterization of ≡(OH)-PSTY28-Br (12)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.5 3 3.5 4 4.5

w (M

)

Log MW

(a) ≡(HO)-PSTY-Br (12)

LND simulation

Figure S20: SEC-RI trace of ≡(OH)-PSTY28-Br (12) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm

9.176

85.761

6.000

2.029

0.989

h

b

c, d,e s, t f, g

a

O

HO

O

OBr

27

a bc d

feg

hs t

Figure S21: 1H 1D DOSY NMR spectrum of ≡(OH)-PSTY28-Br (12) recorded in CDCl3 at 298K (500 MHz).

O

HO

O

O

27

3144.432

0.0

0.5

1.0

1.5

4x10

Inte

ns. [

a.u.

]

2000 3000 4000m/z

3144.432

0.0

0.5

1.0

1.5

4x10

Inte

ns. [

a.u.

]

3000 3100 3200m/z

Expt.= 3144.432, cal. [M+Ag+] = 3144.72M

Figure S22: Full and expanded MALDI-ToF mass spectra of ≡(OH)-PSTY28-Br (12) acquired in reflectron mode with Ag salt as cationizing agent and DCTB matrix.

40

11 Characterization of ≡(OH)-PSTY28-Br (12b)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.6 3.1 3.6 4.1 4.6

w (M

)

Log MW

(a) ≡(HO)-PSTY-Br (12b)

LND simulation

Figure S23: SEC-RI trace of ≡(OH)-PSTY28-Br (12b) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm

9.116

85.694

6.000

1.987

0.977

h

b

c, d,es, t f, g

a

O

HO

O

OBr

27

a bc d

feg

hs t

Figure S24: 1H 1D DOSY NMR spectrum of ≡(OH)-PSTY28-Br (12b) recorded in CDCl3 at 298K (500 MHz).

3144.203

0

2000

4000

6000

8000

Inte

ns. [

a.u.

]

2000 3000 4000 5000 6000m/z

3144.203

0

2000

4000

6000

8000

Inte

ns. [

a.u.

]

3000 3100 3200 3300m/z

Expt.= 3144.203, cal. [M+Ag+] = 3144.72 Expt.= 3162.236, cal. [M+Na+] = 3162.86

O

HO

O

O

27

M

Figure S25: Full and expanded MALDI-ToF mass spectra of ≡(OH)-PSTY28-Br (12b) acquired in reflectron mode with Ag salt as cationizing agent and DCTB matrix.

41

12 Characterization of ≡(OH)-PSTY25-Br (12c)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.5 3 3.5 4 4.5

w (M

)

Log MW

(a) ≡(HO)-PSTY-Br (12c)

LND simulation

Figure S26: SEC-RI trace of ≡(OH)-PSTY25-Br (12c) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.05.5 ppm

9.37

81.07

6.00

2.01

0.98

h

b

f, g

aO

HO

O

OBr

24

a bc d

feg

hs t

Figure S27: 1H 1D DOSY NMR spectrum of ≡(OH)-PSTY25-Br (12c) recorded in CDCl3 at 298K (500 MHz).

0.0

0.2

0.4

0.6

0.8

1.0

4x10

Inte

ns. [

a.u.

]

2000 2500 3000 3500 4000 4500 5000m/z

0.0

0.2

0.4

0.6

0.8

1.0

4x10

Inte

ns. [

a.u.

]

3150 3200 3250 3300 3350 3400m/z

O

HO

O

O

24

Expt.= 3145.72, cal. [M+Ag+] = 3146.16

Expt.= 3164.14, cal. [M+Na+] = 3165.43

Expt.= 3181.73, cal. [M+K+] = 3181.54

Figure S28: Full and expanded MALDI-ToF mass spectra of ≡(OH)-PSTY25-Br (12c), acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

42

13 Characterization of ≡(OH)-PSTY25-N3 (13)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.5 3 3.5 4 4.5

w (M

)

Log MW

(a) ≡(HO)-PSTY-N3 (13)

LND simulation

Figure S29: SEC-RI trace of ≡(OH)-PSTY25-N3 (13) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.05.5 ppm

9.25

78.20

6.00

2.96

c, d, e f, g

b, h

s, t

a

O

HO

O

ON3

24

a bc d

feg

hs t

Figure S30: 1H 1D DOSY NMR spectrum of ≡(OH)-PSTY25-N3 (13) recorded in CDCl3 at 298K (500 MHz).

0.00

0.25

0.50

0.75

1.00

1.25

1.50

4x10

Inte

ns. [

a.u.

]

2950 3000 3050 3100 3150 3200m/z

0.00

0.25

0.50

0.75

1.00

1.25

1.50

4x10

Inte

ns. [

a.u.

]

2000 2500 3000 3500 4000 4500 5000m/z

O

HO

O

ON3

24

Expt.= 3060.84, cal. [M-N2+Ag+] = 3057.03 Expt.= 3084.97, cal. [M+Ag+] = 3085.04

Figure S31: Full and expanded MALDI-ToF mass spectra of ≡(OH)-PSTY25-N3 (13), acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

43

14 Characterization of c-PSTY25-OH (14)

0

0.0001

0.0002

0.0003

0.0004

0.0005

0.0006

0.0007

0.0008

0.0009

2.5 3 3.5 4 4.5

w (M

)

Log MW

(a) ≡(HO)-PSTY-N3 (13)

(b) c-PSTY-OH_crude (14)

(c) c-PSTY-OH_after prep (14)

LND simulation

Figure S32: SEC-RI trace of c-PSTY25-OH (14) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.05.5 ppm

9.18

77.49

6.00

1.98

1.00

N NN

O

OHO

O

24

hb

c, d, e f, g

b

h

c

e

fg s, t

t

d

Figure S33: 1H 1D DOSY NMR spectrum of c-PSTY25-OH (14) recorded in CDCl3 at 298K (500 MHz).

0.0

0.5

1.0

1.5

4x10

Inte

ns. [

a.u.

]

2950 3000 3050 3100 3150 3200m/z

N NN

O

OHO

O

24

0.0

0.5

1.0

1.5

4x10

Inte

ns. [

a.u.

]

2000 2500 3000 3500 4000 4500m/z

Expt.= 3086.87, cal. [M+Ag+] = 3085.09

Figure S34: Full and expanded MALDI-ToF mass spectra of c-PSTY25-OH (14), acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

44

15 Characterization of c-PSTY25-Br (15)

0

0.0001

0.0002

0.0003

0.0004

0.0005

0.0006

0.0007

0.0008

2.5 3 3.5 4 4.5

w (M

)

Log MW

(a) c-PSTY-Br (15)

LND simulation

Figure S35: SEC-RI trace of c-PSTY25-Br (15) based on PSTY calibration curve.

N NN

O

OO

O

24

BrO

1.01.52.02.53.03.54.04.55.05.5 ppm

8.97

77.20

4.00

2.56

2.52

0.85

h b

c, d

f, gb

h

ce

fg

i

i

d

st

s, t

Figure S36: 1H 1D DOSY NMR spectrum of c-PSTY25-Br (15) recorded in CDCl3 at 298K (500 MHz).

0

2000

4000

6000

Inte

ns. [

a.u.

]

3000 3050 3100 3150 3200 3250 3300m/z

0

2000

4000

6000

8000

Inte

ns. [

a.u.

]

2000 2500 3000 3500 4000 4500m/z

N NN

O

OO

O

24

BrO

N NN

O

OO

O

24

O

MALDI

M M1Expt.= 3140.18, cal. [M1+Ag+] = 3139.69

Expt.= 3115.99, cal. [M+Ag+] = 3115.85

Figure S37: Full and expanded MALDI-ToF mass spectra of c-PSTY25-Br (15), acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

45

16 Characterization of c-PSTY25-N3 (16)

0

0.0002

0.0004

0.0006

0.0008

0.001

0.0012

2.5 3 3.5 4

w (M

)

Log MW

(a) c-PSTY-N3, 11c-PSTY25-N3, 16

Figure S38: SEC-RI trace of c-PSTY25-N3 (16) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.05.5 ppm

9.21

79.59

4.00

2.91

1.96

0.97

N NN

O

OO

O

24

N3

O

h b

c, d

f, gb

h

c

e

fg

e, i

i

st

s,t

d

Figure S39: 1H 1D DOSY NMR spectrum of c-PSTY25-N3 (16) recorded in CDCl3 at 298K (500 MHz).

0

2

4

6

4x10

Inte

ns. [

a.u.

]

2000 2500 3000 3500 4000 4500 5000m/z

0

2

4

6

4x10

Inte

ns. [

a.u.

]

2950 3000 3050 3100 3150 3200m/z

N NN

O

OO

O

24

N3

O

Expt=3077.88, cal. [M+Ag+] = 3078.01

Unknown fragmentation

c-PSTY25-N3, 16 Expt.= 3055.37, cal. [M+Ag+] = 3077.88 offset=22.6

Figure S40: Full and expanded MALDI-ToF mass spectra of c-PSTY25-N3 (16), acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

46

17 Characterization of c-PSTY25-≡ (17)

0

0.0002

0.0004

0.0006

0.0008

0.001

2.5 3 3.5 4

w (M

)

Log MW

(a) c-PSTY-≡, 13c-PSTY25-≡, 17

Figure S41: SEC-RI trace of c-PSTY25-≡ (17) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.05.5 ppm

9.03

82.07

4.00

4.90

1.91

2.08

3.95

N NN

O

OO

O

n

NO

OO

OO

NN

h, i, j

h

b

cf

e idg

b

e, m

c,d

g, f

k

j k l

m

l

s, ts

t

Figure S42: 1H 1D DOSY NMR spectrum of c-PSTY25-≡ (17) recorded in CDCl3 at 298K (500 MHz).

0.00

0.25

0.50

0.75

1.00

1.25

1.504x10

Inte

ns. [

a.u.

]

3000 3500 4000 4500 5000m/z

0.00

0.25

0.50

0.75

1.00

1.25

1.504x10

Inte

ns. [

a.u.

]

3500 3550 3600 3650 3700 3750m/z

N NN

O

OO

O

24

NO

OO

OO

NN

c-PSTY25-≡, 17 Expt.= 3530.29, cal. [M+Ag+] = 3530.51

Figure S43: Full and expanded MALDI-ToF mass spectra of c-PSTY25-≡ (17), acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

47

18 Characterization of TIPS-≡-(HO)-PSTY28-Br (18)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.5 3 3.5 4 4.5

w (M

)

Log MW

(a) TIPS-≡(HO)-PSTY-Br (18)

LND simulation

Figure S44: SEC trace of TIPS-≡-(HO)-PSTY28-Br (18) SEC analysis based on polystyrene calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm

31.675

86.453

6.000

2.010

1.004

O

HO

O

OBrSi

27

bc d

fe

h

b

c, d, e

h

f, ga′

g

s t

a′s, t

Figure S45: 500 MHz 1H 1D DOSY NMR spectra in CDCl3 of TIPS-≡-(HO)-PSTY28-Br (18) recorded in CDCl3 at 298K (500 MHz).

3404.617

0.0

0.2

0.4

0.6

0.8

1.0

4x10

Inte

ns. [

a.u.

]

2000 3000 4000 5000m/z

3404.617

0.0

0.2

0.4

0.6

0.8

1.0

4x10

Inte

ns. [

a.u.

]

3300 3400 3500m/z

O

HO

O

OSi

27

Expt.= 3404.617, cal. [M+Ag+] = 3404.92 Expt.= 3422.684, cal. [M+Na+] = 3423.06M

Figure S46: The full and expanded MALDI-ToF mass spectra of TIPS-≡-(HO)-PSTY28-Br (18) acquired in reflectron mode with Ag salt as cationizing agent and DCTB matrix.

48

19 Characterization of TIPS-≡-(OH)-PSTY28-N3 (18b)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.6 3.1 3.6 4.1 4.6

w (M

)

Log MW

(a) TIPS-≡(HO)-PSTY-Br (18b)

LND simulation

Figure S47: SEC-RI trace of TIPS-≡-(HO)-PSTY28-Br (18b) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm

31.694

86.498

6.000

2.018

0.998

O

HO

O

OBrSi

27

bc d

fe

h

b

c, d, e

h

f, ga′

g

s t

a′s, t

Figure S48: 1H 1D DOSY NMR spectrum of TIPS-≡-(HO)-PSTY28-Br (18b) recorded in CDCl3 at 298K (500 MHz).

3304.154

0.0

0.5

1.0

1.5

4x10

Inte

ns. [

a.u.

]

2000 3000 4000 5000m/z

3304.154

0.0

0.5

1.0

1.5

4x10

Inte

ns. [

a.u.

]

3200 3300 3400m/z

Expt.= 3304.154, cal. [M+Ag+] = 3302.86

O

HO

O

O

27

Si

M

Figure S49: Full and expanded MALDI-ToF mass spectra of TIPS-≡-(HO)-PSTY28-Br (18b) acquired in reflectron mode with Ag salt as cationizing agent and DCTB matrix.

49

20 Characterization of TIPS-≡-(HO)-PSTY28-N3 (19)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.5 3 3.5 4 4.5

w (M

)

Log MW

(a) TIPS-≡(HO)-PSTY-N3 (19)

LND simulation

Figure S50: SEC trace of TIPS-≡-(HO)-PSTY28-N3 (19) SEC analysis based on polystyrene calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm

30.363

86.616

6.000

2.987

b, h

c, d, e

f, gs, ta′

O

HO

O

ON3

Si

27

bc d

fe

h

a′

g

s t

Figure S51: 500 MHz 1H 1D DOSY NMR spectra in CDCl3 of TIPS-≡-(HO)-PSTY28-N3 (19) recorded in CDCl3 at 298K (500 MHz).

3631.288

0

500

1000

1500

Inte

ns. [

a.u.

]

3500 3600 3700m/z

O

HO

O

OSi

27N3

MExpt.= 3631.288, cal. [M-N2+Ag+] = 3629.97

3631.288

0

500

1000

1500

Inte

ns. [

a.u.

]

3000 3500 4000 4500 5000m/z

Figure S52: The full and expanded MALDI-ToF mass spectra of TIPS-≡-(HO)-PSTY28-N3 (19) acquired in reflectron mode with Ag salt as cationizing agent and DCTB matrix.

50

21 Characterization of TIPS-≡-(OH)-PSTY28-N3 (19b)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.6 3.1 3.6 4.1 4.6

w (M

)

Log MW

(a) TIPS-≡(HO)-PSTY-N3 (19b)

LND simulation

Figure S53: SEC-RI trace of TIPS-≡-(HO)-PSTY28-N3 (19b) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm

31.681

86.481

6.000

2.984

b, h

c, d, e

f, gs, t

a′

O

HO

O

ON3

Si

28

bc d

fe

h

a′

g

s t

Figure S54: 1H 1D DOSY NMR spectrum of TIPS-≡-(HO)-PSTY28-N3 (19b) recorded in CDCl3 at 298K (500 MHz).

3418.364

0.0

0.2

0.4

0.6

0.8

1.04x10

Inte

ns. [

a.u.

]

3000 4000 5000m/z

3418.364

0.0

0.2

0.4

0.6

0.8

1.04x10

Inte

ns. [

a.u.

]

3300 3350 3400 3450 3500m/z

Expt.= 3418.364, cal. [M-N2+Ag+] = 3417.92

O

HO

O

O

27

Si N3

M

Figure S55: Full and expanded MALDI-ToF mass spectra of TIPS-≡-(HO)-PSTY28-N3 (19b) acquired in reflectron mode with Ag salt as cationizing agent and DCTB matrix.

51

22 Characterization of TIPS-≡(OH-PSTY28)2-Br (20)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.5 3 3.5 4 4.5 5

w (M

)

Log MW


(b) TIPS-≡(HO)-PSTY-N3 (19)

(c) TIPS-≡(OH-PSTY)2-Br (20)

LND simulation

Figure S56: SEC-RI trace of TIPS-≡(OH-PSTY28)2-Br (20) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm

40.004

180.238

12.000

2.407

2.467

0.958

O

HO

O

ON

27

SiNN

O

HO

O

O

27Br

bc d

e fg

h′ b′c d

feg

h

h′

c, d,e

b, b′,h

a′

f, g

s t s ts, t

a′

Figure S57: 1H 1D DOSY NMR spectrum of TIPS-≡(OH-PSTY28)2-Br (20) recorded in CDCl3 at 298K (500 MHz).

6693.163

0

250

500

750

1000

1250

Inte

ns. [

a.u.

]

5000 6000 7000 8000m/z

6693.163

0

250

500

750

1000

1250

Inte

ns. [

a.u.

]

6600 6700 6800m/z

Expt.= 6693.163, cal. [M+Ag+] = 6692.87

O

HO

O

ON

27

SiNN

O

HO

O

O

27

M

Figure S58: Full and expanded MALDI-ToF mass spectra of TIPS-≡(OH-PSTY28)2-Br (20) acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

52

23 Characterization of TIPS-≡(OH-PSTY28)2-Br (20b)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.5 3 3.5 4 4.5 5

w (M

)

Log MW


(b) TIPS-≡(HO)-PSTY-N3 (19b)

(c) TIPS-≡(OH-PSTY)2-Br (20b)

LND simulation

Figure S59: SEC-RI trace of TIPS-≡(OH-PSTY28)2-Br (20b) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm

39.742

180.440

12.000

2.433

2.464

0.958

O

HO

O

ON

27

SiNN

O

HO

O

O

27Br

bc d

e fg

h′ b′c d

feg

h

h′

c, d,e

b, b′,h

a′

f, g

s t s ts, t

a′

Figure S60: 1H 1D DOSY NMR spectrum of TIPS-≡(OH-PSTY28)2-Br (20b) recorded in CDCl3 at 298K (500 MHz).

O

HO

O

ON

27

SiNN

O

HO

O

O

27

6692.757

0

250

500

750

1000

1250

Inte

ns. [

a.u.

]

6600 6700 6800m/z

6692.757

0

250

500

750

1000

1250

Inte

ns. [

a.u.

]

6000 7000 8000m/z

Expt.= 6692.757, cal. [M+Ag+] = 6691.87Expt.= 6713.541, cal. [M+Na+] = 6714.03M

Expt.= 6727.461, cal. [M1+Na+] = 6728.04

Figure S61: Full and expanded MALDI-ToF mass spectra of TIPS-≡(OH-PSTY28)2-Br (20b) acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

53

24 Characterization of TIPS-≡(OH-PSTY28)2-N3 (21)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.5 3 3.5 4 4.5 5

w (M

)

Log MW



(c) TIPS-≡(OH-PSTY)2-N3 (21)

LND simulation

(A)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.5 3 3.5 4 4.5 5

w (M

)

Log MW




LND simulation

(B)

Figure S62: SEC-RI traces of TIPS-≡(OH-PSTY28)2-N3 (21) crude (a) and purified (b) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm

40.031

180.121

12.000

3.317

1.635

0.986

h′

c, d,eb, b′,h

f, g

s, t a′

O

HO

O

ON

27

SiNN

O

HO

O

O

27N3

bc d

e fg

h′ b′c d

feg

hs t s t

a′

Figure S63: 1H 1D DOSY NMR spectrum of TIPS-≡(OH-PSTY28)2-N3 (21) recorded in CDCl3 at 298K (500 MHz).

54

6320.222

0

1

2

3

4x10

Inte

ns. [

a.u.

]

6000 7000 8000m/z

6320.222

0

1

2

3

4x10

Inte

ns. [

a.u.

]

6200 6300 6400m/z

Expt.= 6293.615, cal. [M-N2+Ag+] = 6294.86

O

HO

O

ON

27

SiNN

O

HO

O

O

27N3

MExpt.= 6320.222, cal. [M+Ag+] = 6320.64

Figure S64: Full and expanded MALDI-ToF mass spectra of TIPS-≡(OH-PSTY28)2-N3 (21) acquired in linear mode with Ag salt as cationizing agent and DCTB matrix..

55

25 Characterization of TIPS-≡(OH-PSTY28)2-N3 (21b)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.6 3.1 3.6 4.1 4.6

w (M

)

Log MW



(c) TIPS-≡(OH-PSTY)2-N3 (21b)

LND simulation

Figure S65: SEC-RI trace of TIPS-≡(OH-PSTY28)2-N3 (21b) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm39.537

180.360

12.000

3.325

1.624

0.958

O

HO

O

ON

27

SiNN

O

HO

O

O

27N3

bc d

e fg

h′ b′c d

feg

h

h′

c, d,eb, b′,h

a′

f, g

s t s ts, t a′

Figure S66: 1H 1D DOSY NMR spectrum of TIPS-≡(OH-PSTY28)2-N3 (21b) recorded in CDCl3 at 298K (500 MHz).

6942.445

0

1000

2000

3000

4000

Inte

ns. [

a.u.

]

5000 6000 7000 8000m/z

6942.445

0

1000

2000

3000

4000

Inte

ns. [

a.u.

]

6800 6900 7000m/z

Expt.= 6942.445, cal. [M+Ag+] = 6943.01Expt.= 6916.981, cal. [M-N2+Ag+] = 6916.01

O

HO

O

ON

27

SiNN

O

HO

O

O

27N3

M

Figure S67: Full and expanded MALDI-ToF mass spectra of TIPS-≡(OH-PSTY28)2-N3 (21b) acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

56

26 Characterization of TIPS-≡(Br-PSTY28)2-N3 (22)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.5 3 3.5 4 4.5 5

w (M

)

Log MW



(c) TIPS-≡(Br-PSTY)2-N3 (22)

LND simulation

Figure S68: SEC-RI trace of TIPS-≡(Br-PSTY28)2-N3 (22) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm

45.506

180.102

8.000

4.989

5.926

0.966

O

O

O

ON

27

SiNN

O

O

O

O

27N3

O

Br

O

Br

b, b′, ie, h

c,d

g, fs, t

bc d

e fg

h′b′

c d

feg

hs t s t

i

a

h′

a′

Figure S69: 1H 1D DOSY NMR spectrum of TIPS-≡(Br-PSTY28)2-N3 (22) recorded in CDCl3 at 298K (500 MHz).

7113.538

0.0

0.5

1.0

4x10

Inte

ns. [

a.u.

]

6000 7000 8000m/z

7113.538

0.00

0.25

0.50

0.75

1.00

1.25

4x10

Inte

ns. [

a.u.

]

7000 7100 7200m/z

MExpt.= 7113.538, cal. [M+Ag+] = 7113.37

O

O

O

ON

27

SiNN

O

O

O

O

27N3

O

Br

O

Br

Expt.= 7084.756, cal. [M-N2+Ag+] = 7085.36

Figure S70: Full and expanded MALDI-ToF mass spectra of TIPS-≡(Br-PSTY28)2-N3 (22) acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

57

27 Characterization of TIPS-≡(Br-PSTY28)2-N3 (22b)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.6 3.1 3.6 4.1 4.6

w (M

)

Log MW



(c) TIPS-≡(Br-PSTY)2-N3 (22b)

LND simulation

(A)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.6 3.1 3.6 4.1 4.6

w (M

)

Log MW



(c) TIPS-≡(Br-PSTY)2-N3 (22b)LND simulation

(B)

Figure S71: SEC-RI trace of TIPS-≡(Br-PSTY28)2-N3 (22b) crude (a) and purified (b) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm

46.711

181.353

8.000

4.975

5.915

0.973

O

O

O

ON

27

SiNN

O

O

O

O

27N3

O

Br

O

Br

b, b′, ie, h

c,d

g, fs, t

bc d

e fg

h′b′

c d

feg

hs t s t

i

a

h′

a′

Figure S72: 1H 1D DOSY NMR spectrum of TIPS-≡(Br-PSTY28)2-N3 (22b) recorded in CDCl3 at 298K (500 MHz).

58

7004.150

0

1000

2000

3000

Inte

ns. [

a.u.

]6000 7000 8000 9000

m/z

7004.150

0

500

1000

1500

2000

2500

3000

Inte

ns. [

a.u.

]

6900 7000 7100m/z

Expt.= 7004.150, cal. [M+Ag+] = 7003.76

M

O

O

O

ON

27

SiNN

O

O

O

O

27N3

O

Br

O

Br

Expt.= 6978.282, cal. [M-N2+Ag+] = 6975.75

Figure S73: Full and expanded MALDI-ToF mass spectra TIPS-≡(Br-PSTY28)2-N3 (22b) acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

59

28 Characterization of TIPS-≡(N3-PSTY28)2-N3 (23)

1.01.52.02.53.03.54.04.55.0 ppm

44.979

180.864

8.000

8.965

1.969

1.000

O

O

O

ON

27

SiNN

O

O

O

O

27N3

O

N3

O

N3

b′

b, e, h, i c,d

g, fs, tbc d

e fg

h′b′

c d

feg

hs t s t

i

a

h′

a′

Figure S74: 1H 1D DOSY NMR spectrum of TIPS-≡(N3-PSTY28)2-N3 (23) recorded in CDCl3 at 298K (500 MHz).

6724.156

0

1000

2000

3000

4000

5000

Inte

ns. [

a.u.

]

6000 7000 8000m/z

6724.156

0

1000

2000

3000

4000

Inte

ns. [

a.u.

]

6600 6700 6800m/z

Expt.= 6724.156, cal. [M+Ag+] = 6725.15

O

O

O

ON

27

SiNN

O

O

O

O

27N3

O

N3

O

N3

Expt.= 6696.417, cal. [M-N+Na+] = 6696.95M

Figure S75: Full and expanded MALDI-ToF mass spectra of TIPS-≡(N3-PSTY28)2-N3 (23) acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

60

29 Characterization of TIPS-≡(HO-PSTY28)3-Br (24)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.5 3 3.5 4 4.5 5

w (M

)

Log MW


(b) TIPS-≡(HO-PSTY)2-N3 (21)

(c) TIPS-≡(OH-PSTY)3-Br (24)

LND simulation

Figure S76: SEC-RI trace of TIPS-≡(HO-PSTY28)3-Br (24) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm51.829

270.192

18.000

2.318

4.524

1.936

O

HO

O

ON

27

SiNN

O

HO

O

O

27N

NN

O

HO

O

O

27Br

a′

bc d

e fg

h′b′

c d

feg

b′c d

feg

h

h′

b, b′,h

c, d, e

h′

f, g

s t s t s t

s, t

a′

Figure S77: 1H 1D DOSY NMR spectrum of TIPS-≡(HO-PSTY28)3-Br (24) recorded in CDCl3 at 298K (500 MHz).

Expt.= 10194.213, cal. [M+Ag+] = 10194.19

O

HO

O

ON

27

SiNN

O

HO

O

O

27N

NN

O

HO

O

O

27

M

10194.213

0

2000

4000

6000

Inte

ns. [

a.u.

]

9000 10000 11000 12000m/z

10194.213

0

2000

4000

6000

Inte

ns. [

a.u.

]

10100 10200 10300m/z

Figure S78: Full and expanded MALDI-ToF mass spectra of TIPS-≡(HO-PSTY28)3-Br (24) acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

61

30 Characterization of TIPS-≡(HO-PSTY28)3-N3 (25)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.5 3 3.5 4 4.5 5

w (M

)

Log MW




LND simulation(A)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.5 3 3.5 4 4.5 5

w (M

)

Log MW




LND simulation

(B)

Figure S79: SEC-RI trace of TIPS-≡(HO-PSTY28)3-N3 (25) crude (a) and purified (b) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm

51.036

270.270

18.000

4.047

3.167

1.935

O

HO

O

ON

27

SiNN

O

HO

O

O

27N

NN

O

HO

O

O

27N3

a′

bc d

e fg

h′b′

c d

feg

b′c d

feg

h

h′b, b′,h

c, d, e

h′

f, g

s t s t s t

s, ta′

Figure S80: 1H 1D DOSY NMR spectrum of TIPS-≡(HO-PSTY28)3-N3 (25) recorded in CDCl3 at 298K (500 MHz).

62

10652.621

0

100

200

300

400

500

Inte

ns. [

a.u.

]

10500 10600 10700m/z

Expt.= 10652.621, cal. [M+Ag+] = 10653.82

O

HO

O

ON

27

SiNN

O

HO

O

O

27N

NN

O

HO

O

O

27N3

M

10652.621

0

100

200

300

400

500

Inte

ns. [

a.u.

]

10000 11000 12000m/z

Expt.= 10632.765, cal. [M-N+Ag+] = 10630.21

Figure S81: Full and expanded MALDI-ToF mass spectra of TIPS-≡(HO-PSTY28)3-N3 (25) acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

63

31 Characterization of TIPS-≡(Br-PSTY28)3-N3 (26)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.5 3 3.5 4 4.5 5

w (M

)

Log MW



(c) TIPS-≡(Br-PSTY)3-N3 (26)

LND simulation

Figure S82: SEC-RI trace of TIPS-≡(Br-PSTY28)3-N3 (26) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm57.843

270.387

12.000

6.956

8.931

1.963

O

O

O

ON

27

SiNN

O

O

O

O

27N

NN

O

O

O

O

27N3

O

Br

O

Br

O

Br

b, b′, ie, h

c,d

g, fs, t a

h′

bc d

e fg

h′b′

c d

feg

b′c d

feg

hh′s t s t s t

ia′

TIPS-≡(Br-PSTY28)3-N3, 26

Figure S83: 1H 1D DOSY NMR spectrum of TIPS-≡(Br-PSTY28)3-N3 (26) recorded in CDCl3 at 298K (500 MHz).

10537.034

0

1000

2000

3000

4000

Inte

ns. [

a.u.

]

9000 10000 11000 12000m/z

10537.034

0

1000

2000

3000

4000

Inte

ns. [

a.u.

]

10400 10500 10600m/z

O

O

O

ON

27

SiNN

O

O

O

O

27N

NN

O

O

O

O

27N3

O O

Br Br

O

Br

Expt.= 10537.034, cal. [M+Ag+] = 10537.95Expt.= 10509.591, cal. [M-N2+Ag+] = 10509.54

M

Figure S84: Full and expanded MALDI-ToF mass spectra of TIPS-≡(Br-PSTY28)3-N3 (26) acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

64

32 Characterization of TIPS-≡(N3-PSTY28)3-N3 (27)

1.01.52.02.53.03.54.04.55.0 ppm

48.133

270.793

12.000

11.967

3.995

2.001

O

O

O

ON

27

SiNN

O

O

O

O

27N

NN

O

O

O

O

27N3

O

N3

O

N3

O

N3

b′

b, e, h, i c,d

g, fs, t a

h′

bc d

e fg

h′b′

c d

feg

b′c d

feg

hh′s t s t s t

ia′

Figure S85: 1H 1D DOSY NMR spectrum of TIPS-≡(N3-PSTY28)3-N3 (27) recorded in CDCl3 at 298K (500 MHz).

10737.131

0

250

500

750

1000

1250

Inte

ns. [

a.u.

]

9000 10000 11000 12000m/z

10737.131

0

250

500

750

1000

1250

Inte

ns. [

a.u.

]

10600 10700 10800m/z

Expt.= 10737.131, cal. [M+Ag+] = 10736.75

O

O

O

ON

27

SiNN

O

O

O

O

27N

NN

O

O

O

O

27N3

O O

N3 N3

O

N3 MExpt.= 10714.034, cal. [M-N+Ag+] = 10713.16

Figure S86: Full and expanded MALDI-ToF mass spectra of TIPS-≡(N3-PSTY28)3-N3 (27) acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

65

33 Characterization of TIPS-≡(HO-PSTY28)3-HO-(PSTY28-OH)3-≡-TIPS (28)

0

0.00005

0.0001

0.00015

0.0002

0.00025

3.2 3.7 4.2 4.7

w (M

)

Log MW

(a) TIPS-≡(HO-PSTY)3-N3 (25)

(b) TIPS-≡(HO-PSTY)3-HO-(HO-PSTY)3-≡-TIPS (28)LND simulation

Figure S87: SEC-RI trace of TIPS-≡(HO-PSTY28)3-HO-(PSTY28-OH)3-≡-TIPS (28) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm99.943

540.162

42.000

4.625

11.411

6.002

O

HO

O

ON

27

SiNN

O

HO

O

O

27N

NN

O

HO

O

O

27N

NN

O

HO

ON

N N

O

OH

O

ON

27

SiN N

O

OH

O

O

27N

N N

O

OH

O

O

27

h′

b, b′c, d, e

s, ta′

b c d

e fg

h′s t

a′

b′

g, f

Figure S88: 1H 1D DOSY NMR spectrum of TIPS-≡(HO-PSTY28)3-HO-(PSTY28-OH)3-≡-TIPS (28) recorded in CDCl3 at 298K (500 MHz).

20460.454

0

250

500

750

1000

1250

Inte

ns. [

a.u.

]

20400 20500 20600m/z

Expt.= 20460.454, cal. [M+Na+] = 20461.21M

O

HO

O

ON

27

SiNN

O

HO

O

O

27N

NN

O

HO

O

O

27N

NN

O

HO

ON

N N

O

OH

O

ON

27

SiN N

O

OH

O

O

27N

N N

O

OH

O

O

27

20460.454

0

500

1000

1500

Inte

ns. [

a.u.

]

18000 20000 22000m/z

Figure S89: Full and expanded MALDI-ToF mass spectra of TIPS-≡(HO-PSTY28)3-HO-(PSTY28-OH)3-≡-TIPS (28) acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

66

34 Characterization of TIPS-≡(Br-PSTY28)3-Br-(Br-PSTY28)3-≡-TIPS (29)

0

0.00005

0.0001

0.00015

0.0002

0.00025

3.2 3.7 4.2 4.7

w (M

)

Log MW

(a) TIPS-≡(HO-PSTY)3-N3 (25)

(b) TIPS-≡(Br-PSTY)3-Br-(Br-PSTY)3-≡-TIPS (29)LND simulation

Figure S90: SEC-RI trace of TIPS-≡(Br-PSTY28)3-Br-(PSTY28-Br)3-≡-TIPS (29) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm

120.198

540.732

28.000

14.047

22.969

6.001

O

O

O

ON

27

SiNN

O

O

O

O

27N

NN

O

O

O

O

27N

NN

O

O

ON

N N

OO

ON

27

SiN N

OO

O

27N

N N

OO

O

27

O

Br

O

Br

O

Br

O

Br

O O OO

Br

O

Br

O

Br

h′

i, b, b′c, d

s, t a′

b c d

e fg

h′s t

a′

b′

g, f

i

e

Figure S91: 1H 1D DOSY NMR spectrum of TIPS-≡(Br-PSTY28)3-Br-(PSTY28-Br)3-≡-TIPS (29) recorded in CDCl3 at 298K (500 MHz).

O

O

O

ON

27

SiNN

O O

O

27N

NN

O

O

O

O

27N

NN

O ON

N N

O

O

O

ON

27

SiN N

O

O

O

O

27N

N N

O

O

O

O

27

O

Br

O

Br

OO

Br

O

Br

O

Br

O

Br

OO

Br

M

21711.706

-200

0

200

400

Inte

ns. [

a.u.

]

19000 20000 21000 22000 23000m/z

21711.706

0

100

200

300

400

500

Inte

ns. [

a.u.

]

21600 21650 21700 21750m/z

Expt.= 21711.706, cal. [M+Na+] = 21710.95

Figure S92: Full and expanded MALDI-ToF mass spectra of TIPS-≡(Br-PSTY28)3-Br-(PSTY28-Br)3-≡-TIPS (29) acquired in linear mode with Ag salt as cationizing agent and DCTB matrix.

67

35 Characterization of TIPS-≡(N3-PSTY28)3-N3-(PSTY28-N3)3-≡-TIPS (30)

1.01.52.02.53.03.54.04.55.0 ppm

120.076

540.580

28.000

24.981

11.993

6.002

O

O

O

ON

27

SiNN

O

O

O

O

27N

NN

O

O

O

O

27N

NN

O

O

ON

N N

OO

ON

27

SiN N

OO

O

27N

N N

OO

O

27

O

N3

O

N3

O

N3

O

N3

O O OO

N3

O

N3

O

N3

h′

b, e, i c, d

s, t a′

b c d

e fg

h′s t

a′

b′

g, f

i

b′

Figure S93: 1H 1D DOSY NMR spectrum of TIPS-≡(N3-PSTY28)3-N3-(PSTY28-N3)3-≡-TIPS (30) recorded in CDCl3 at 298K (500 MHz).

21561.851

1000

2000

3000

4000

Inte

ns. [

a.u.

]

21400 21500 21600 21700m/z

Expt.= 21561.851, cal. [M-N+Na+] = 21562.69

O

O

O

ON

27

SiNN

O

O

O

O

27N

NN

O

O

O

O

27N

NN

O

O

ON

N N

OO

ON

27

SiN N

OO

O

27N

N N

OO

O

27

O

N 3

O

N3

O

N3

O

N3

O O OO

N3

O

N3

O

N 3

M

21561.851

-1000

0

1000

2000

3000

4000

Inte

ns. [

a.u.

]

20000 21000 22000 23000m/z

Figure S94: Full and expanded MALDI-ToF mass spectra of TIPS-≡(N3-PSTY28)3-N3-(PSTY28-N3)3-≡-TIPS (30) acquired in linear mode with Ag salt as cationizing agent and DCTB matrix..

68

36 Characterization of tri-cyclic architecture (31)

1.01.52.02.53.03.54.04.55.05.5 ppm

98.729

396.155

16.000

18.006

10.163

21.959

O

O

O

ON

27

SiNN

O

O

O

O

27

O O

N

O

O

O

NN

O

NN

N

NNN

O

O

O

O

O

24

h, i, jc, d

s, t f, g, a

e

c d

fi

e

s t

j

b

g

hba

b

ji

Figure S95: 1H 1D DOSY NMR spectrum of tricyclic architecture (31) recorded in CDCl3 at 298K (500 MHz).

69

37 Characterization of tri_dendron architecture (32)

1.01.52.02.53.03.54.04.55.05.5 ppm

126.502

859.628

38.000

4.166

27.909

13.992

O

O

O

ON

27

SiNN

O

O

O

O

27

O O

O

O

O

O

NN N

O

ON

N NO

ON

N NO

NNN

19

27

27

h, ib

c, d, k

s, tf, g, a

e

c d

fi

e

s t

b

b

g

h

kg

b ha

Figure S96: 1H 1D DOSY NMR spectrum of tri_dendron architecture (32) recorded in CDCl3 at 298K (500 MHz).

38 Characterization of tetra_cyclic architecture (33)

1.01.52.02.53.03.54.04.55.05.5 ppm

119.198

641.004

28.000

22.537

14.241

29.712

O

O

O

ON

27

SiNN

O

O

O

O

27

O O

O

O

O

O

27

O

NNN

N

O

O

O

NN

O

NN

N

NNN

O

O

O

O

O

24

h, i, jc, d

s, t f, g, a

e

c d

fi

e

s t

j

b

g

hba

b

ji

Figure S97: 1H 1D DOSY NMR spectrum of tetra_cyclic architecture (33) recorded in CDCl3 at 298K (500 MHz).

70

39 Characterization of tetra_dendron architecture (34)

1.01.52.02.53.03.54.04.55.05.5 ppm

166.643

1174.449

52.000

5.936

38.687

17.973

O

O

O

ON

27

SiNN

O

O

O

O

27

O O

O

O

O

O

27

O

NNN

O

O

O

O

NN N

O

ON

N NO

ON

N NO

NNN

19

27

27

h, ib

c, d, k

s, tf, g, a

e

c d

fi

e

s t

b

b

g

h

kg

b h'a

Figure S98: 1H 1D DOSY NMR spectrum of tetra_dendron architecture (34) recorded in CDCl3 at 298K (500 MHz).

40 Characterization of hepta_cyclic architecture (35)

1.01.52.02.53.03.54.04.55.05.5 ppm

241.192

1050.306

56.000

28.001

20.493

55.942

O

O

O

ON

27

SiNN

O

O

O

O

27N

NN

O

O

O

O

27N

NN

O

O

ON

N N

OO

ON

27

SiN N

OO

O

27N

N N

OO

O

27

O O OO O O

O O OO

N

O

O

O

NN

O

NN

N

NNN

O

O

O

O

O

24

h, i, jc, d

s, t f, g, a

e

c d

fi

e

s t

j

b

g

hba

b

ji

Figure S99: 1H 1D DOSY NMR spectrum of hepta_cyclic architecture (35) recorded in CDCl3 at 298K (500 MHz).

41 Characterization of hepta_dendron architecture (36)

O

O

O

ON

27

SiNN

O

O

O

O

27N

NN

O

O

O

O

27N

NN

O

O

ON

N N

OO

ON

27

SiN N

OO

O

27N

N N

OO

O

27

O O OO O O

O O OO

O

O

O

O

NN N

O

ON

N NO

ON

N NO

NNN

19

27

27

h, ib

c, d, k

s, t f, g, a

Figure 40: 400 MHz 1H NMR spectra in CDCl3 of Six block dendrimer, 36.

e

c d

fi

e

s t

b

b

g

h

kg

ba

1.01.52.02.53.03.54.04.55.05.5 ppm

296.709

2229.107

98.000

14.537

72.443

33.795

Figure S100: 1H 1D DOSY NMR spectrum of hepta_dendron architecture (36) recorded in CDCl3 at 298K (500 MHz).

71

42 Characterization of TIPS-≡(HO-PSTY28)2-≡ (37)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.6 3.1 3.6 4.1 4.6

w (M

)

Log MW

(a) ≡(HO)-PSTY-Br (12b)(b) TIPS-≡(HO)-PSTY-N3 (19b)(c) TIPS-≡(HO-PSTY)2-≡ (37)LND simulation

(A)

0

0.0001

0.0002

0.0003

0.0004

0.0005

2.6 3.1 3.6 4.1 4.6

w (M

)

Log MW



(c) TIPS-≡(Br-PSTY)2-N3 (22b)LND simulation

(B)

Figure S101: SEC-RI trace of TIPS-≡(HO-PSTY28)2-≡ (37) crude (a) and purified (b) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.05.5 ppm

40.774

172.976

12.000

3.997

3.994

1.974

O

HO

O

ON

29

SiNN

O

HO

O

O

29N

NN O

bc d

e fg

h′b′

c d

feg

h’

h′

c, d,eb, b′, i, j

a′

f, g

s t s ts, t

a′ij

k

k

Figure S102: 1H 1D DOSY NMR spectrum of TIPS-≡(HO-PSTY28)2-≡ (37) recorded in CDCl3 at 298K (500 MHz).

72

7037.470

0

1000

2000

3000

4000

5000

Inte

ns. [

a.u.

]

6000 7000 8000m/z

7037.470

0

1000

2000

3000

4000

5000

Inte

ns. [

a.u.

]

6900 7000 7100m/z

Expt.= 7037.470, cal. [M+Ag+] = 7038.06

O

HO

O

ON

27

SiNN

O

HO

O

O

27N

NN O

Expt.= 7057.377, cal. [M+Na+] = 7059.21Expt.= 7072.077, cal. [M+K+] = 7071.17

M

Figure S103: Full and expanded MALDI-ToF mass spectra of TIPS-≡(HO-PSTY28)2-≡ (37) acquired in linear mode with Ag salt as cationizing agent and DCTB matrix..

73

43 Characterization of TIPS-≡(Br-PSTY28)2-(HO-PSTY28)2-≡-TIPS (38)

0

0.00005

0.0001

0.00015

0.0002

0.00025

0.0003

0.00035

3 3.5 4 4.5 5

w (M

)

Log MW

(a) TIPS-≡(HO-PSTY)2-≡ (37)

(b) TIPS-≡(Br-PSTY)2-N3 (22b)

(c) TIPS-≡(Br-PSTY)2-(HO-PSTY)2-≡-TIPS (38)

LND simulation

Figure S104: SEC-RI trace of TIPS-≡(Br-PSTY28)2-(HO-PSTY28)2-≡-TIPS (38) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm84.740

429.061

20.000

3.892

18.292

3.906

O

HO

O

ON

27

SiNN

O

HO

O

O

27N

NN

OO

O

O

ON

27

SiN N

O

O

O

O

27

O

Br

O

Br

N NN

bc d

e fg

h′s t

a′

b′

i

e’

b, b′, e, ie'

c,d,e

g, fs, t

a'

h′

b

Figure S105: 1H 1D DOSY NMR spectrum of TIPS-≡(Br-PSTY28)2-(HO-PSTY28)2-≡-TIPS (38) recorded in CDCl3 at 298K (500 MHz).

74

44 Characterization of TIPS-≡(N3-PSTY28)2-(HO-PSTY28)2-≡-TIPS (39)

0

0.00005

0.0001

0.00015

0.0002

0.00025

0.0003

0.00035

3 3.5 4 4.5 5

w (M

)

Log MW



(c) TIPS-≡(N3-PSTY)2-(HO-PSTY)2-≡-TIPS (39)

LND simulation

(A)

0

0.00005

0.0001

0.00015

0.0002

0.00025

0.0003

0.00035

3 3.5 4 4.5 5

w (M

)

Log MW



(c) TIPS-≡(N3-PSTY)2-(HO-PSTY)2-≡-TIPS (39)

LND simulation

(B)

Figure S106: SEC-RI trace of TIPS-≡(N3-PSTY28)2-(HO-PSTY28)2-≡-TIPS (39) crude (a) and purified (b) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.0 ppm

86.412

401.056

20.000

5.975

15.950

3.861

O

HO

O

ON

27

SiNN

O

HO

O

O

27N

NN

OO

O

O

ON

27

SiN N

O

O

O

O

27

O

N3

O

N3

N NN

bc d

e fg

h′s t

a′

b′

i

e’

b, b′, ei,e'

c,d,e

g, fs, t a'

h′

b

Figure S107: 1H 1D DOSY NMR spectrum of TIPS-≡(N3-PSTY28)2-(HO-PSTY28)2-≡-TIPS (39) recorded in CDCl3 at 298K (500 MHz).

75

45 Characterization of TIPS-≡(Dendron-PSTY28)2-(HO-PSTY28)2-≡-TIPS (40)

0

0.00005

0.0001

0.00015

0.0002

0.00025

0.0003

0.00035

3 3.5 4 4.5 5

w (M

)

Log MW

(a) (PSTY)2-PSTY-≡ (11)

(b) TIPS-≡(N3-PSTY)2-(HO-PSTY)2-≡-TIPS (39)

(c) TIPS-≡(Dendron-PSTY)2-(HO-PSTY)2-≡-TIPS (40)LND simulation

Figure S108: SEC-RI trace of TIPS-≡(Dendron-PSTY28)2-(HO-PSTY28)2-≡-TIPS (40) based on PSTY calibration curve.

1.01.52.02.53.03.54.04.55.05.5 ppm

142.300

835.956

40.000

3.950

27.954

11.897

O

O

O

ON

29

SiNN

O

O

O

O

29

O O

O

O

O

O

NN N

O

ON

N NO

ON

N NO

NNN

19

27

27

N NNO

O

OH

O

ON

29

SiN N

O

OH

O

O

29N NN

bc d

e fg

h′s t

a′

b

ie’

b

b

kg

h, i

c, d, k, e’

f, g, a

e

b

s,t

Figure S109: 1H 1D DOSY NMR spectrum of TIPS-≡(Dendron-PSTY28)2-(HO-PSTY28)2-≡-TIPS (40) recorded in CDCl3 at 298K (500 MHz).

76

46 Characterization of TIPS-≡(Dendron-PSTY28)2-(Br-PSTY28)2-≡-TIPS (41)

0

0.00005

0.0001

0.00015

0.0002

0.00025

0.0003

0.00035

3 3.5 4 4.5 5

w (M

)

Log MW

(a) (PSTY)2-PSTY-≡ (11)

(b) TIPS-≡(N3-PSTY)2-(HO-PSTY)2-≡-TIPS (39)

(c) TIPS-≡(Dendron-PSTY)2-(Br-PSTY)2-≡-TIPS (41)LND simulation

Figure S110: SEC-RI trace of TIPS-≡(Dendron-PSTY28)2-(Br-PSTY28)2-≡-TIPS (41) based on PSTY calibration curve.

0.51.01.52.02.53.03.54.04.55.0 ppm

151.347

838.524

35.849

7.813

29.695

11.670

O

O

O

ON

29

SiNN

O

O

O

O

29

O O

O

O

O

O

NN N

O

ON

N NO

ON

N NO

NNN

19

27

27

N NNO

O

O

O

ON

29

SiN N

O

O

O

O

29N NN

O

Br

O

Br

bc d

e fg

hs t

a

b

ie

b

b

kg

h, i c, d, k,

f, g, a

eb,i’

s,ti'

Figure S111: 1H 1D DOSY NMR spectrum of TIPS-≡(Dendron-PSTY28)2-(Br-PSTY28)2-≡-TIPS (41) recorded in CDCl3 at 298K (500 MHz).

77

47 Characterization of TIPS-≡(Dendron-PSTY28)2-(N3-PSTY28)2-≡-TIPS (42)

O

O

O

ON

29

SiNN

O

O

O

O

29

O O

O

O

O

O

NN N

O

ON

N NO

ON

N NO

NNN

19

27

27

N NNO

O

O

O

ON

29

SiN N

O

O

O

O

29N NN

O

N3

O

N3

bc d

e fg

h′s t

a′

b

ie

b

b

kg

h, ic, d, k,

f, g, a

e,i’b

s,ti'

1.01.52.02.53.03.54.04.55.0 ppm

145.150

831.933

36.000

9.992

28.005

11.996

Figure S112: 1H 1D DOSY NMR spectrum of TIPS-≡(Dendron-PSTY28)2-(N3-PSTY28)2-≡-TIPS (42) recorded in CDCl3 at 298K (500 MHz).

78

49 Characterization of TIPS-≡(Dendron-PSTY28)2-(Cyclic-PSTY28)2-≡-TIPS (43)

1.01.52.02.53.03.54.04.55.05.5 ppm

185.016

976.693

40.000

12.029

32.156

25.919

O

O

O

ON

29

SiNN

O

O

O

O

29

O O

O

O

O

O

NN N

O

ON

N NO

ON

N NO

NNN

19

27

27

N NNO

O

O

O

ON

29

SiN N

O

O

O

O

29N NN

O O

N

O

O

O

NN

O

NN

N

NNN

O

O

O

O

O

24

bc d

e fg

hs t

a′

b

ie’

b

b

kg

h, i, jc, d, k,

f, g, a

eb

s,ti

Figure S113: 1H 1D DOSY NMR spectrum of TIPS-≡(Dendron-PSTY28)2-(Cyclic-PSTY28)2-≡-TIPS (43) recorded in CDCl3 at 298K (500 MHz).

REFERENCES

1. Hossain, M. D.; Jia, Z. F.; Monteiro, M. J. Macromolecules 2014, 47, (15), 4955-4970.

2. Jia, Z. F.; Lonsdale, D. E.; Kulis J.; Monteiro, M. J. ACS Macro Lett. 2012, 1, (6), 780-783

Linear Polymer Chain. · 1 Supporting Information to Precise Grafting of Macrocyclics and Dendrons...

Documents

Transcript of Linear Polymer Chain. · 1 Supporting Information to Precise Grafting of Macrocyclics and Dendrons...