Pill 5 H and G SI

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Proton Transfer in HostGuest Complexation Between A

Difunctional Pillar[5]arene and Alkyldiamines

Guocan Yu,* Bin Hua and Chengyou Han

Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China.

Email address: [email protected].

Supporting Information (20 pages)

1. Materials and methods S2

2. Synthesis of H S2

3. 1H NMR studies of hostguest complexation between Hand the guests S9

4. ITC investigations of hostguest complexation between Hand the guests S10

5. ESI-MS spectra of the hostguest complexes S13

6. 2D NOESY spectra of the hostguest complexes S157. ITC investigations of hostguest complexation between DMP5and G1 S18

8. Single crystal structure of HG1and HG4 S19

9. X-ray crystal data forHG1 S20

10. X-ray crystal data forHG4 S20


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2. Synthesis of H

Scheme S1.Synthetic route to 1.

Synthesis of 2: Methyl chloroacetate (2.59 g, 24.0 mmol) and K2CO3 (6.62 g, 48.0

mmol) were added to a solution of 1 (2.17 g, 3.00 mmol) in CH3CN (50 mL). The

mixture was heated in a three-necked flask under nitrogen atmosphere at reflux for 24

h. The cooled reaction mixture was filtered and washed with chloroform. The filtrate

was evaporated under vacuum, and the residue was purified by crystallization in a

mixture of methanol and chloroform. The product 2 was collected by filtration,

washed with methanol, and dried under vacuum (2.36 g, 91%). Mp 153 .5155.1 C.

The proton NMR spectrum of 2 is shown in Figure S1. 1H NMR (400 MHz,

chloroform-d, room temperature) (ppm): 6.81 (s, 2H), 6.80 (s, 4H), 6.78 (s, 2H),6.66 (s, 2H), 4.50 (s, 4H), 3.77 (t, J= 4 Hz, 10H), 3.72 (s, 6H), 3.70 (s, 6H), 3.68 (s,

6H), 3.64 (s, 6H), 3.08 (s, 6H). The 13C NMR spectrum of2is shown in Figure S2.

13C NMR (100 MHz, chloroform-d, room temperature) (ppm): 169.78, 150.68,

150.56, 150.52, 149.49, 128.75, 128.42, 128.33, 128.15, 127.81, 114.59, 114.42,

113.84, 113.78, 113.67, 65.87, 55.86, 55.76, 55.73, 55.64, 51.45, 29.72, 29.41.

LRESIMS is shown in Figure S3: m/z889.5 [M + Na]+(100%). HRESIMS: m/z calcd

for [M + H]+C49H55O14, 867.3514, found 867.3529, error 2 ppm.


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Figure S1.1H NMR spectrum (400 MHz, chloroform-d, room temperature) of 2.

Figure S2.13C NMR spectrum (100 MHz, chloroform-d, room temperature) of 2.


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Figure S3.Electrospray ionization mass spectrum of 2. Assignment of the main peak: m/z

889.5 [M + Na]+

.

Synthesis of H: A solution of 2 (1.73 g, 2.00 mmol) in CH3CH2OH (120 mL) was

treated with 40% aqueous sodium hydroxide (120 mL) at reflux for 12 h. The mixture

was concentrated under reduced pressure, diluted with water (20 mL), and acidified

with HCl. The precipitated product was collected by filtration, washed with water, and

dried under vacuum to give H (1.56 mg, 93%) as a white solid, mp 139.5141.8 C.

The proton NMR spectrum of H is shown in Figure S4. 1H NMR (400 MHz,

chloroform-d, room temperature) (ppm): 6.77 (s, 2H), 6.76 (s, 2H), 6.74 (s, 2H),

6.67 (s, 2H), 6.65 (s, 2H), 4.52 (s, 4H), 3.82 (s, 4H), 3.77 (s, 6H), 3.68 (d, J= 1.2 Hz,

12H), 3.65 (d,J= 4 Hz, 12H). The 13C NMR spectrum ofHis shown in Figure S5.

13C NMR (125 MHz, chloroform-d, room temperature) (ppm): 170.73, 151.55,

150.88, 150.74, 150.25, 149.03, 129.14, 128.92, 128.30, 128.02, 127.53, 115.68,

114.73, 114.47, 114.15, 113.91, 65.85, 57.08, 56.07, 56.04, 55.99, 30.20, 29.72, 29.34.

LRESIMS is shown in Figure S6: m/z837.1 [M H](100%). HRESIMS: m/z calcd

for [M H]C47H49O14, 837.3201, found 837.3220, error 2 ppm.


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Figure S4.1H NMR spectrum (400 MHz, chloroform-d, room temperature) of H.

Figure S5.13C NMR spectrum (100 MHz, chloroform-d, room temperature) of H.


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Figure S6. Electrospray ionization mass spectrum of copillar[5]arene 1 in a mixture ofdichloromethane and methanol.Assignment of main peaks: m/z837.1 [M H]

(100%).

Figure S7.HMBC spectrum of H.

Figure S8.HMQC spectrum of H.


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Figure S9.DEPT-135 spectrum of H.

Figure S10.2D COSY spectrum of H.


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3. 1H NMR investigation of hostguest complexation between Hand the guests

Figu re S11.1H NMR spectra (500 MHz, chloroform-d/methanol-d4 = 1:1, 295 K): (a) G1

(5.00 mM); (b) H(5.00 mM) and G1(5.00 mM); (c) H(5.00 mM); (d) H(5.00 mM) and G3

(5.00 mM), (e)G3(5.00 mM); (f)G5(5.00 mM); (g)H(5.00 mM) and G5(5.00 mM); (h) H

(5.00 mM).

Figu re S12.1H NMR spectra (500 MHz, chloroform-d/methanol-d4 = 1:1, 295 K): (a) G2

(5.00 mM); (b) H(5.00 mM) and G2(5.00 mM); (c) H(5.00 mM); (d) H(5.00 mM) and G4

(5.00 mM), (e)G4(5.00 mM); (f)G6(5.00 mM); (g)H(5.00 mM) and G6(5.00 mM); (h) H

(5.00 mM).


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4. ITC investigations of hostguest complexation between Hand the guests

As confirmed by ITC investigations, the hostguest complexations in these

systems were all exothermic, and the entropy changes were all negative, so we draw

the conclusion that the complexations were driven by enthalpy changes.

Figu re S13.Microcalorimetric titration of G1(2.00 mM, 10 L per injection) with H(0.100mM) in the mixture of chloroform and methanol (1:1, v/v) at 303.15 K.



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5. ESI-MS spectra of the hostguest complexes

151.0

242.4

318.4

413.4

471.4619.7

877.3

941.4

1112.2

+MS, 0.0-0.1min (#2-#9)

0.00

0.25

0.50

0.75

1.00

1.25

6x10

Intens.

200 400 600 800 1000 1200 1400 1600 m/z

Figu re S19.Electrospray ionization mass spectrum of HG1.Assignment of the main peak:m/z941.4 [H+ G1+ H]+, 471.4 [H+ G1+ 2H]2+.



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114.3

485.5

861.2969.2

+MS, 0.0-0.2min (#1-#17)

0

1

2

3

4

6x10

Intens.

200 400 600 800 1000 1200 1400 m/z

Figu re S21.Electrospray ionization mass spectrum of HG3.Assignment of the main peak:m/z969.2 [H+ G3+ H]

+

, 485.5 [H+ G3+ 2H]2+

.




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Figu re S24.Electrospray ionization mass spectrum of HG6.Assignment of the main peak:m/z1011.7 [H+ G6+ H]

+

, 506.3 [H+ G6+ 2H]2+

.

6. 2D NOESY spectra of the hostguest complexes

Figu re S25.Partial NOESY NMR spectrum (500 MHz, chloroform-d/methanol-d4= 1:1, 295K) of H(5.00 mM) and G1(5.00 mM).


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7. ITC investigations of hostguest complexation between DMP5and G1

By introducing two carboxylic acid groups into the pilla[5]arene, proton transfer

from the carboxylic acid groups to the amine units could occur in the principle of

undergoing an acid-base reaction. Compared with the 1,4-dimethoxypillar[5]arene

(DMP5), the association constants for the hostguest inclusion complexes (HG)

were enhanced significantly, which was ascribe to the cooperativity of electrostaticinteractions, multiple C-H interactions and hydrogen bonds.


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Figu re S31.Microcalorimetric titration of G1 (2.00 mM, 10 L per injection) with DMP5

(0.100 mM) in the mixture of chloroform and methanol (1:1, v/v) at 303.15 K.

8. Single crystal structure of HG1and HG4

Figu re S32. Views of the crystal structures of HG1 (a and c) and HG4 (b and d).

Hydrogens except the ones participating in the formation of C-H interactions and


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hydrogen bonds were omitted for clarity. The purple dotted lines indicate C-H interactions

and hydrogen bonds.

9. X-ray crystal data forHG1

Crystallographic data: colorless, C54H72N2O16,FW1005.14, monoclinic, space groupP21/n, a

= 20.356 (17),b= 12.726 (8), c= 20.992 (13) , = 90.00, = 108.03 (3), = 90.00, V=

5171.2 (6) 3, Z = 4, Dc = 1.291 g cm3, T = 170 K, = 0.095 mm1, 20046 measured

reflections, 9454 independent reflections, 667 parameters, 55 restraints,F(000) = 2152,R1=

0.2141, wR2= 0.4278 (all data),R1= 0.1334, wR2= 0.3574 [I > 2(I)], max. residual density

1.569 e3

, and goodness-of-fit (F2

) = 1.288. CCDC 916495

10. X-ray crystal data for HG4

Crystallographic data: colorless, C56H78N2O17, FW 1051.20,orthorhombic, space groupP212121, a= 12.1923(5),b= 18.8559(8), c= 24.0835(10) , = 90.00, = 90.00, =

90.00, V = 5536.7(4) 3,Z = 4, Dc = 1.261 g cm3, T = 170 K, = 0.093 mm1, 25593

measured reflections, 5584 independent reflections, 701 parameters, 4 restraints, F(000) =

2256, R1 = 0.0523, wR2 = 0.0981 (all data), R1 = 0.0397, wR2 = 0.0912 [I > 2(I)], max.

residual density 0.324 e3, and goodness-of-fit (F2) = 1.021.CCDC 916493

References:

S1. (a) Han, C.; Gao, L.; Yu, G.; Zhang, Z.; Dong, S.; Huang, F.Eur. J. Org. Chem. 2013,

25292532. (b) Han, C.; Zhang, Z.; Yu, G.; Huang, F. Chem. Commun. 2012, 48,

98769878.

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