Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905;...

Coordination Polymers/

Metal-Organic Frameworks

Christoph Janiak

University of Düsseldorf, Germany

Email: janiak@uni-duesseldorf.de

Periodic, extended architectures/framework structures

collagen fiber from parallel

collagen fibrils:

function

Periodic, extended architectures/framework structures,diatoms:

Periodic, extended architectures/framework structures

Collembola

(springtails)

surface structure:

(tooth)

enamel prisms:

Metal-organic networks / Coordination polymers

bridging organic ligand

M M M M1D chains

2D nets

M M MM

MM3Dframeworks

From metal-organic networks

to hydrogen-bonded Networks

D = hydrogen donorA = hydrogen acceptor

Metal-organic networks H-bonded networks

M M M M1D chains

2D nets

M M MM

MM3Dframeworks

covalent

less flexible

more directional

network

electrostatic

more flexible

less directional

network

Metal-organic networks:

Nodal properties of metal and ligands

Metal ions or metal-ligand fragments with free coordination sites

M M MM

bridging ligands

1D chain

2D net

3D framework

James,

Chem. Soc. Rev.

2003, 32, 276

Eddaoudi et al.,

Acc. Chem. Res.

2001, 34, 319

Oxtoby et al.

PNAS 2002,

99, 4905;

Eddaoudi et al.,

PNAS 2002,

99, 4901

Coordination polymers:

M M MM

bridging ligands

1D chain

2D net

3D framework

James,

Chem. Soc. Rev.

2003, 32, 276

Eddaoudi et al.,

Acc. Chem. Res.

2001, 34, 319

Oxtoby et al.

PNAS 2002,

99, 4905;

Eddaoudi et al.,

PNAS 2002,

99, 4901

M M MM

bridging ligands

1D chain

2D net

3D framework

James,

Chem. Soc. Rev.

2003, 32, 276

Eddaoudi et al.,

Acc. Chem. Res.

2001, 34, 319

Oxtoby et al.

PNAS 2002,

99, 4905;

Eddaoudi et al.,

PNAS 2002,

99, 4901

M M MM

bridging ligands

1D chain

2D net

3D framework

James,

Chem. Soc. Rev.

2003, 32, 276

Eddaoudi et al.,

Acc. Chem. Res.

2001, 34, 319

Oxtoby et al.

PNAS 2002,

99, 4905;

Eddaoudi et al.,

PNAS 2002,

99, 4901

4,4'-bipyridine

pyrazineO

oxalate

benzene-1,4-dicarboxylate,terephthalate

benzene-1,3,5-tricarboxylate,trimesate

hexamethylene-tetramine

isonicotinate

tetra(4-cyanophenyl)methanetetra(4-carboxyphenyl)methane

D = –CN

–CO2–

N2,4,6-tris(4-pyridyl)-1,3,5-triazine

Examples of linear, trigonal and tetrahedral ligands

linear rigid

trigonal

tetrahedral

linear flexible

possible)

Oxtoby et al., PNAS 2002, 99, 4905; Kitagawa, Masaoka, Coord. Chem. Rev. 2003, 246, 73;

Barnett, Champness, Coord. Chem. Rev. 2003, 246, 145; Zheng et al., Coord. Chem. Rev. 2003, 246, 185;

Ye et al., Coord. Chem. Rev. 2005, 249, 545; Zhang, Chen, Chem. Commun. 2006, 1689

Metal-organic networks / Metal-organic frameworks (MOFs):

Application-oriented properties

Dalton Trans.

(Review)

2003, 2781

Conductivity

Non-linear optics

M M... ...

...M... ...

M M... ...

M... ...

Catalysis

Chirality

Luminescence

Magnetism

Porosity

Zeolitic behavior

Spin-crossover

New J. Chem. 2010, 34, 2366

Coordination polymers / Metal-organic frameworks (MOFs):

A dynamic field

New J. Chem. 2010, 34, 2366

Interests in coordination polymers

crystal engineeringanion control

solvent control

ligands

architecture

helices

chirality

catalysis

hydrothermal synthesis

interpenetration

NLO-effects, -materials

polymorphism

(nano/micro-) porosity

zeolite analogs

molecular magnets

sensors

electrical conductivity

from structure to function

spin-crossover

noncovalent interactions

enantioselectivity

molecular sieves

ligandsupramolecular

interactions

solvent

temperature

time stoichiometry

concentration

periodicmolecular-based

architecture

reaction/crystallization conditions

Our approach:

From molecular building blocks to periodic, extended architectures

construction aspects:

Crystallization from molecular building blocks in solution

solution

solvent

solution

solvent/solution

reaction time, days

temperature

autoclave forhydrothermal synthesis

Coordination polymers with

multidentate ligands

additional functionality,

framework structure with anchor groups

JCS Dalton Trans. 1999, 183; JCS Dalton Trans. 1999, 3121.

The concept:

NNC CN

Introduction

pyrazolylborate ligands

Trofimenko, Scorpionates, Imperial College Press, London 1999

hydro-tris(pyrazolyl)borate dihydro-bis(pyrazolyl)borate

- molecular chelate complexes

KBH4 + n H-azolyl K[H4-nB(azolyl)n] + n H2

Modified poly(pyrazolyl)borate ligands

tris(pyrazolyl)borate

bis(triazolyl)borate

tris(indazolyl)borate

tris(triazolyl)borate

bis(tetrazolyl)borate

Chem. Commun. 1994, 545; Chem. Eur. J. 1995, 1, 637; Z. Anorg. Allg. Chem. 2000, 626, 2053

endodentate

chelating tometal atoms

molecularcomplexes

exodentate

bridgingbetween

metal atoms

networks

Coordination polymers from

modified poly(pyrazolyl)borato ligands

tris(triazolyl)borateN3

bis(tetrazolyl)borateN4

-0.11 -0.09-0.13

charge distribution(AM1-calculation)

modified poly(pyrazolyl)borate ligands

·4H2O

·1.5H2O

Chem. Eur. J. 1995, 1, 637.

JCS Dalton Trans. 1994, 2947.

water substructure

Chem. Eur. J. 1995, 1, 637.

C-H...O/N hydrogen bonding

Chem. Eur. J. 1995, 1, 637

Chem. Eur. J. 1996, 2, 991

Polyhedron 2002, 21, 553

linkage isomers

3-D coordination polymer

Zn2+ + 2 N3-

days months

chelate complex

J. Chem. Soc. Dalton Trans. 1994, 2947

H2O H2O

6 H2O 1.5 H2O

kinetic product thermodynamic product

porous 3-D coordination polymer ?

Tl (Tl)

modified poly(pyrazolyl)borate ligands

M = Mn, Fe, Co (Ni, Cu), Zn, Cd

Polyhedron 2002, 21, 553.

Chem. Eur. J. 1995, 1, 637.

with bis(triazolyl)borate

continuing work by

Lobbia, Pettinari et al.

JCS Dalton Trans. 2002, 2333;

Inorg. Chim. Acta 2005, 358, 1162.

Youm et al., Bull. Kor. Chem. Soc.

2006, 27, 1521.

Metal-N4

symmetric versus distorted grids

M = Mn,Fe,Co,Zn,Cd M = Ni,Cu

crystallization from H2O crystallization from NH3/H2O

aqua ligands ammine ligands

crystal water no crystal water

Chem. Eur. J. 1995, 1, 637

Chem. Ber. 1995, 128, 323

Metal-N4

the water substructure as a reinforcing bar

Chem. Ber. 1995, 128, 323

from structure to function

space group: P 21cn (Pna 21)

Nfunction: 2nd order NLO effect (frequency doubling)

J. Am. Chem. Soc. 1996, 118, 6307

SHG signal intensity: 2 W/cm2

(1064 to 532 nm)

coefficient:

d33 = 1/2 ccc = (6±3)·10-15

indices of refraction:

(at 532 nm)

nc = 1.661

na = 1.584

structure: 2-D coordination polymer

Metal-organic networks:2[Ag(µ-HB(C2H2N3)3]

Non-linear optics b

1064 nm

532 nm non-centrosymmetric

space group: Pna 21

JACS 1996, 118, 6307

SHG: 2 W/cm2

d33 = 1/2 ccc = (6±3)·10–15 m/V

Non-linear optics

CO2–

N CO2– N

CO2–

+ Zn2+

, Cd2+

Evan, Lin,

Acc. Chem. Res. 2002, 35, 211

Dalton Trans. 2003, 2781

Coordination polymers with multidentate ligands

additional functionality

J. Chem. Soc., Dalton Trans. 1999, 183

Synthesis 1999, 959

Synth. Commun. 1999, 29, 3341

NNC CN

5,5'-dicyano-2,2'-bipyridine

N NNC CN

+ Ag-saltsvariation of anionvariation of solvents

Coordination polymers

with modified 4,4'-bipyridine ligands

Coordination polymers with multidentate ligands:

Control elements for metal-ligand coordination

chelating

bidentate tetradentatetridentate

N NNC CN

NCanion

1D-chain

NC CN AgAg

2D-netanion

"non"-coordinating

BF4–, PF6

–coordinating

NO3–, CF3SO3

–"non"-coordinating

PF6–

solvent

EtOH/THF

MeCN/EtOH/CH2Cl2

solvent

MeCN/EtOH/

toluene

Effect of solvent changes

molecular chelatecomplex

2D coordination polymer

N NNC CN

NC CN AgAg

2D-netanion

"non"-coordinating

BF4–, PF6

–"non"-coordinating

PF6–

Understanding?

Design at will?

solvent

EtOH/THF

MeCN/EtOH/CH2Cl2

solvent

MeCN/EtOH/

toluene

32.62 Kagomé net

2D Coordination polymer:2[Ag(µ3-L)]PF6·1/2C6H5CH3

32.62 Kagomé net

2D Coordination polymer:2[Ag(µ3-L)]PF6·1/2C6H5CH3

4,4'-bipyridine

2,2'-dimethyl-4,4'-bipyrimidine

2,2'-bi-1,6-naphthyridine

Synthesis, 1999, 959

charge distribution(AM1 calculation)

-0.14-0.13

+ M-saltsvariation of Mvariation of anionvariation of conditions

2,2'-dimethyl-4,4'-bipyrimidine

chelatingbidentate tetradentate

bridgingtridentate

MMNN N

J. Chem. Soc. Dalton Trans. 1999, 3121

M = NiII

+ Cl–/OH2

+ I–

+ NO3–

+ I–

+ PF6–

+ NO3–

coordinating anion "non"-coordinating anion

+ heat + RT

different thermal treatment

Bodar-Houillon et al.,

Inorg. Chem.

1995, 34, 5205

2[Cu2(µ3-I)2(µ-L)]

2[Ag3(NCCH3)3(µ3-L)](PF6)3

63 net

2[Ag3(NCCH3)3(µ3-L)](PF6)3

63 net

Coordination polymers with multidentate ligands

additional functionality

M = CoII, ZnII, CdII

N NN N M

"non"-coordinating anion

CuI+ PF6–+ NCS–

coordinating anion

Chem. Commun. 1998, 2637

2,2'-bi-1,6-naphthyridine

bidentate bridging tridentate

2-D Coordination polymers with binaphthyridine:

Interpenetration

M = CoII, ZnII, CdII

15.8 - 16 Å

2-D coordination polymers with binaphthyridine

interpenetration

3.25 Å

2-D coordination polymers with binaphthyridine

interpenetration

3.25 Å

Interpenetration

1D 1D 3D 3D

3D 3D 3D 3D

Batten, Robson,

Angew. Chem. Int. Ed. 1998, 37, 1460

Carlucci, Ciani, Proserpio

2D 2D 2D 2D

Spin-crossover

FeFe Fe

low-spin

high-spin

Temp. increase,green light,

pressure decrease

Temp. decrease,red light,

pressure increase

van Koningsbruggen,

Top. Curr. Chem.

2004, 233, 123.

Dalton Trans.

(Review)

2003, 2781.

Haasnoot,

Coord. Chem. Rev.

2000, 200–202, 131.

+ Fe2+

+ NCS–

+ EtOH

Spincrossover

Spin-crossover

Kepert et al.,

Science 2002, 298, 1762

Porosity

Spin-crossover – cooperative behavior

FeFe Fe

Gütlich et al.,

Eur. J. Inorg. Chem. 2007, 4481.

Example of recent work:

[{Fe(tba)3}X2]·nH2O

btre1,2-bis(1,2,4-triazol-4-yl)ethane

possiblebridging mode:

Metal-organic networks

with bridging bis(1,2,4-triazolyl)-ligands

Our choice:

spin-crossover,

magnetic interactions

with appropriate

metal atoms

rarely used so far: 2{M(NCS)2(µ2-btre-kN1,N1')2(NCS)2} (M = Fe, Co)

3{[Cu3(µ4-btre-kN1,N2,N1',N2')2(µ3-btre-kN1,N2,N1')4(H2O)2]2(ClO4)12·2H2O}

Garcia, Gütlich et al., Inorg. Chem. 2005, 44, 9723.

Garcia, Haasnoot, Kahn et al. Eur. J. Inorg. Chem. 2000, 307.

1,2-bis(1,2,4-triazol-1-yl)ethane

1,4-bis(1,2,4-triazol-1-yl)butane

1,4-bis(1,2,4-triazol-1-ylmethyl)benzene

1,3-bis(1,2,4-triazol-1-yl)propane

N NNM M

with bridging bis(1,2,4-triazol-1-yl)-ligands

Examples of recent work:

Zhu et al., J. Coord. Chem. 2006, 59, 513.

Wang et al., Chem. Eur. J. 2006, 12, 2680.

Frequently used bis-triazolyl ligands:

Wang et al., Acta Cryst. 2007, E63, m2416.

Peng et al., Cryst. Growth&Des. 2006, 6, 994.

Tian et al., Inorg. Chem. 2008, 47, 3274.

fluconazole

N NN M

with bridging bis(1,2,4-triazolyl)-ligands

Frequently used bis-triazolyl ligands:

Li, Ma, Su et al., Dalton Trans. 2008, 3824.

Dalton Trans. 2008, 2015.

Inorg. Chem. 2007, 46, 8283.

Han et al., Eur. J. Inorg. Chem. 2006, 1594.

btre1,2-bis(1,2,4-triazol-4-yl)ethane

with 1,2-bis(1,2,4-triazol-4-yl)ethane

N H2O, 180 °C, 3d ZnX2

X = Cl, Br, ClO4, (SO4)1/2

Cu(II) Cu(I)

0D, 1D, 2D, 3D networks

N H2O, 180 °C, 3d X = Cl, Br, ClO4, (SO4)1/2

Cu(II) Cu(I)

Example for 1D:

Cu(II) Cu(I)

Example for 1D:

- - - interstrand C-H···N

Inorg. Chem. 2009, 48, 2166.

Example for 2D:

Cu(II) Cu(I)

2D 2[Cu2(µ2-Cl)2(µ4-btre)]

Example for 2D:

Cu(II) Cu(I)

2D 2[Cu2(µ2-Cl)2(µ4-btre)]- - - interlayer C-H···Cl

-stacking

Inorg. Chem. 2009, 48, 2166.

Examples for 3D:

Cu(II) Cu(I)

3D 3{[Cu(µ4-btre)]ClO4 · ~0.25H2O}

ClO4–, H2O

Inorg. Chem. 2009, 48, 2166.

Cu(II) Cu(I)

0D, 1D, 2D, 3D networks oxidative ligand decomposition

formation of cyanide

3D interpenetrated nets

3D 3[Cu2(µ2-CN)2(µ4-btre)]

Inorg. Chem. 2009, 48, 2166.

N H2O, 180 °C, 3dZnX2

X = Cl, Br, ClO4, (SO4)1/2

Cu(II) Cu(I)

0D, 1D, 2D, 3D networks oxidative ligand decomposition

formation of cyanide

3D interpenetrated nets

interpenetration control through stacking

Inorg. Chem. 2009, 48, 2166.

1,2-bis(1,2,4-triazol-4-yl)ethane networks:

Structure – solid-state CPMAS 13C NMR correlation

(bold = occ. fact. 1)

Inorg. Chem. 2009, 48, 2166.

(bold = occ. fact. 1)

(normal = occ. fact. 0.5)

Porosity and zeolitic behavior

M M MM

Zeolitic behaviorPorosity

– ab/desorption, gas storage

– ion exchange

– enantiomer separation

– selective catalysis

Eddaoudi et al., Acc. Chem. Res. 2001, 34, 319;

Kesanli, Lin, Coord. Chem. Rev. 2003, 246, 305;

Rao et al., Angew. Chem. Int. Ed. 2004, 43, 1466;

Kitagawa et al., Angew. Chem. Int. Ed. 2004, 43, 2334;

Kitagawa, Uemura, Chem. Soc. Rev. 2005, 34, 109;

Rowsell, Yaghi, Angew. Chem. Int. Ed. 2005, 44, 4670;

Mueller et al., J. Mater. Chem. 2006, 16, 626;

Kepert, Chem. Commun. 2006, 695;

Kitagawa et al. Chem. Commun. 2006, 701;

Porosity and zeolitic behavior

Zeolitic behaviorPorosity

+ {Zn4(µ4-O)(MeOH)4}

O. M. Yaghi et al., Science 2002, 2003

Rowsell, Yaghi, Angew. Chem. Int. Ed., 2005, 117, 4670

Schröder, Champness et al., CrystEngComm, 2007, 9, 438

CH4, H2 storage

Mixed-ligand metal-organic networks:3{[Ni3(µ3-L1)2(µ4-L2)2(µ-H2O)2]·~22H2O}

O–OL1 =

potential solvent volume

1621 Å3/unit cell

(H2O ~40 Å3)

Porosity ?

O–OL1 =Porosity ?

R1/wR2 [>2(I)] 0.0398 / 0.1076

R1/wR2 (all) 0.0473 / 0.1125

Some of the disordered O positions refined isotropically

with "anti-bumping" restraints (BUMP).

Occupancies refined to about 0.15, 0.30, 0.60, 0.90 and 1.000,

summed up to 22 O atoms per Ni3

3{[Ni3(µ3-L1)2(µ4-L2)2(µ-H2O)2]·~22H2O} – careful drying

3{[Ni3(µ2-L1)2(µ4-L2)2(µ-H2O)2(H2O)2]·4H2O}

Porosity ?

solid state crystal to-

crystal transformation

under vacuum

Porosity

O–OL1 =

but ...

b = 13.5328(2) Å

b = 8.2320(5) Å

Mixed-ligand coordination polymers:3{[Zn3(µ4-L1)2(µ4-L2)2(H2O)2]·2H2O}

potential solvent volume

94 Å3/unit cell

(H2O ~40 Å3)

O–OL1 =

Porosity ?

3{[Zn3(µ4-L1)2(µ4-L2)2(H2O)2]·2H2O} – careful drying

3{[Zn3(µ5-L1)2(µ4-L2)2]·~0.67H2O}

Porosity ?

solid state

single-crystal

to-single-crystal

transformation

between 100-280 °C

Porosity

O–OL1 =

O–OL1 =but ...

flexible framework,

dynamic porous properties

150 °C/12 hPa

40 °C/56 hPa

–H2O

for dynamic porous properties, see Kitagawa, Uemura, Chem. Soc. Rev. 2005, 34, 109.

Stefan Henninger

J. Am. Chem. Soc. 2009, 131, 2776.

Principle process in an adsorption chiller

Stefan Henninger

J. Am. Chem. Soc. 2009, 131, 2776.

Adsorption chillers: Water loading lifts

Stefan Henningerzeolites

J. Am. Chem. Soc. 2009, 131, 2776.

Magnetism

organic ligands for stronger magnetic coupling:

nitronyl nitroxide

radical

N NO O

pyrazolate

carboxylate

2,2'-bipyrimidine

oxalate

Batten, Murray,

Coord. Chem. Rev.

2003, 246, 103.

Maspoch et al.,

J. Mater. Chem.

2004, 14, 2713.

Maspoch, et al,

Chem. Soc. Rev.,

2007, 36, 770.

Magnetism

organic ligands for stronger magnetic coupling:

nitronyl nitroxideradical

N NO O

pyrazolate

carboxylate

2,2'-bipyrimidine

oxalate

triazolate

triazole

Batten, Murray,

Coord. Chem. Rev.

2003, 246, 103

Maspoch et al.,

J. Mater. Chem.

2004, 14, 2713

Maspoch, et al,

Chem. Soc. Rev.,

2007, 36, 770

Magnetism

= Mn(II) = Cr(III)

anionic net: [MIIMIII(ox)3]–C

Example:

Dalton Trans.

2003, 2781

Batten, Murray,

Coord. Chem. Rev.

2003, 246, 103

Maspoch et al.,

J. Mater. Chem.

2004, 14, 2713

Maspoch, et al,

Chem. Soc. Rev.,

2007, 36, 770

Magnetic interactions based on triazole ligands

Cl(Br)

Example of recent work:

Drabent et al., Inorg. Chem. 2008, 47, 3358.

{[Cu(μ-OH)(μ-ClPhtrz)][(H2O)(BF4)]}n

ClPhtrz

constructed from triazolate ligands

triazolate

Zhang, X.M. Chen, Chem. Commun.

(Review) 2006, 1689.

Barea, Sironi et al., Dalton Trans. 2008, 1825,

R = Et

Recent examples

R2tz –

{Cu(H2tz)}n

{Cu(Et2tz)}n

Magnetism

intra-Ni3 trimer antiferromagnetic coupling with J = –13.88(8) cm–1

O–OL1 =

Mixed-ligand metal-organic networks:3{[Cu4(µ5-L1)2(µ3-OH)2(µ4-L2)]·2H2O}

Cu1Cu2'

Cu2Cu1'

2J32J1

chair-shaped or

stepped-cubane Cu4O4

2J1 = 258 cm–1,

2J2 = –416 cm–1,

2J3 = 484 cm–1

antiferromagnetic coupling, three pathways

with Joaquin Sanchiz

Magnetism

2∞[Cu2(µ5-btb)(µ-OH)(µ-H2O)]

with ferromagnetically coupled Cu2 units

Magnetism

J = 83(1) cm–1

j2 = 0.161(1) cm–1

O–Obtb =

with J. Sanchiz, Dalton Trans. 2008, 4877.

Luminescence

Eu Gd Tb

Zheng, Chen, Aust. J. Chem. 2004, 57, 703

Luminescence

Mixed-ligand metal-organic networks :3{[Zn3(µ4-L1)2(µ4-L2)2(H2O)2]·2H2O}

Luminescence

O–OL1 =

Mixed-ligand coordination polymers:2∞{[Cu2(µ-L-tryptophanato)2(µ-4,4'-bipyridine)(H2O)2](NO3)2}

Chirality

Mixed-ligand coordination polymers:2∞{[Cu2(µ-L-tryptophanato)2(µ-4,4'-bipyridine)(H2O)2](NO3)2}

Chirality

Coordination polymers as catalysts

Lit.: [RuCl2(PPh3)3]

[RuCl2(L)3/2]

L = P P

Catalysis

[RuCl2(PPh3)3]: R. L. Chowdhury, J.-E. Bäckvall, Chem. Commun. 1991, 1063.

3 .5 0 4 .0 0 4 .5 0 5 .0 0 5 .5 0 6 .0 0 6 .5 00

5 0 0 0 0

1 0 0 0 0 0

1 5 0 0 0 0

2 0 0 0 0 0

2 5 0 0 0 0

3 0 0 0 0 0

3 5 0 0 0 0

4 0 0 0 0 0

4 5 0 0 0 0

T im e -->

A b u n d a n c eT IC : T H O M A S 1 5 .D

t = 1.5 h

O+Toluol

(int. stand.)

3 .5 0 4 .0 0 4 .5 0 5 .0 0 5 .5 0 6 .0 0 6 .5 00

5 0 0 0 0

1 0 0 0 0 0

1 5 0 0 0 0

2 0 0 0 0 0

2 5 0 0 0 0

3 0 0 0 0 0

3 5 0 0 0 0

4 0 0 0 0 0

T im e -->

A b u n d a n c eT IC : T H O M A S 1 9 .D

t = 7.5 h

[RuCl2(L)3/2]

– GC-MSOHH

0 5 10Time [h]

Catalysis

catalyst recycling after t = 6 h

[RuCl2(L)3/2]OOH

[RuCl2(L)3/2]

0 1 2 3 4 5 6 7 8 9 10 11

Recycling [no.]

]Recycling Exp A

Recycling Exp B

Catalysis

- homochiral- chiral 1D channels- 47% free volume

+ ROH CH3C(O)OR +

2{[2H3O][Zn3(µ3-O)L6]·12H2O}

NO2CH3C(O)O

NO2HOA

Catalysis and chirality

Porosity

Catalysis Chirality

Zeolitic behavior

Kim et al., Nature 2000, 404, 982

Kesanli, Lin,

Coord. Chem. Rev.

2003, 246, 305

Summary:

O–OL1 =

mixed-ligand

benzene-1,2,3-carboxylate

Magnetism

structure – CPMAS 13C NMR correlation

Luminescence

crystal-to-

crystal

transition

Summary:

O–OL1 =

mixed-ligand

crystal-to-

crystal

transition

Summary:

Metal-organic networks: Application-oriented properties

Conductivity

Non-linear optics

M M... ...

...M... ...

M M... ...

M... ...

Catalysis

Chirality

Luminescence

Magnetism

Porosity

Zeolitic behavior

Spin-crossover

Summary:

Metal-organic networks: Application-oriented properties

Conductivity

Non-linear optics

M M... ...

...M... ...

M M... ...

M... ...

Catalysis

Chirality

Luminescence

Magnetism

Porosity

Zeolitic behavior

Spin-crossover

Acknowledgements

CPMAS NMR Dr. Anke Hoffmann, Univ. Freiburg

Magnetism Prof. J. Sanchiz, Univ. La Laguna

Mössbauer Dr. H. Winkler, Univ. Lübeck

TG/MS PD Dr. C. Näther, Univ. Kiel

Neutron diffraction Dr. S. Mason, ILL Grenoble

Heat transformation S. Henninger, ISE Freiburg

Luminescence Dr. H. Höppe, Univ. Freiburg

special X-ray Prof. C. Röhr, Univ. Freiburg

NP-TEM Dr. R. Thomann, Univ. Freiburg

Au-NP Dr. M. Krüger, Dr. M. Walter, Univ. Freiburg

Finances: DFG, FCI, AvH

Dr. Khalid Abu-Shandi

Frederik Blank

Anne-Christine Chamayou

Stefan Deblon

Dr. Thomas Dorn

Prof. Dr. M. Enamullah (AvH)

Marie Genitrini

Jerôme Krämer

Dr. Paul G. Lassahn

Hesham Mena

Dr. Barbara Wisser (née Paul)

Engelbert Redel

Dr. Tobias Scharmann

Dr. Savas Temizdemir

Lars Uehlin

Jana Vieth

Christian Vollmer

Dr. Biao Wu

Dr. He-Ping Wu (AvH)

Dr. Xiao-Juan Yang

Dr. Cungen Zhang (AvH)

Coordination Polymers/ Metal-Organic Frameworks...2001, 34, 319 Oxtoby et al. PNAS 2002, 99, 4905;...

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