The development in the field of coordination polymers or metal-organic coordination networks, MOCNs (metal-organic frameworks, MOFs) is assessed in terms of property investigations in the areas of catalysis, chirality, conductivity, luminescence, magnetism, spin-transition (spin-crossover), non-linear optics (NLO) and porosity or zeolitic behavior upon which potential applications could be based.

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Engineering coordination polymers towards applications

: The unpolarized absorption and circular dichroism spectra of the fundamental vibrational transitions of the chiral molecule, 4-methyl-2-oxetanone, are calculated ab initio. Harmonic force fields are obtained using Density Functional Theory (DFT), MP2, and SCF methodologies and a 5S4P2D/3S2P (TZ2P) basis set. DFT calculations use the Local Spin Density Approximation (LSDA), BLYP, and Becke3LYP (B3LYP) density functionals. Mid-IR spectra predicted using LSDA, BLYP, and B3LYP force fields are of significantly different quality, the B3LYP force field yielding spectra in clearly superior, and overall excellent, agreement with experiment. The MP2 force field yields spectra in slightly worse agreement with experiment than the B3LYP force field. The SCF force field yields spectra in poor agreement with experiment.The basis set dependence of B3LYP force fields is also explored: the 6-31G* and TZ2P basis sets give very similar results while the 3-21G basis set yields spectra in substantially worse agreements with experiment. jg

Ab initio calculation of vibrational absorption and circular dichroism spectra using density functional force fields

Coordination polymer networks with O- and N-donors: What they are, why and how they are made

This review (over 380 references) summarizes metal–organic frameworks (MOFs), Materials Institute Lavoisier (MILs), iso-reticular metal–organic frameworks (IR-MOFs), porous coordination networks (PCNs), zeolitic metal–organic frameworks (ZMOFs) and porous coordination polymers (PCPs) with selected examples of their structures, concepts for linkers, syntheses, post-synthesis modifications, metal nanoparticle formations in MOFs, porosity and zeolitic behavior for applications in gas storage for hydrogen, carbon dioxide, methane and applications in conductivity, luminescence and catalysis.

MOFs, MILs and more: concepts, properties and applications for porous coordination networks (PCNs)

Metal-organic molecular architectures with 2,2′-bipyridyl-like and carboxylate ligands

In this paper three coordination polymers, {[Fe(fcz)2Cl2]·2CH3OH}n (1), {[Cu(fcz)2(H2O)]·SO4·DMF·2CH3OH·2H2O}n (2), and {[Cu(fcz)2Cl2]·2CH3OH}n (3) {fcz = 1-(2,4-difluorophenyl)-1,1-bis[(1H-1,2,4-triazol-l-yl)methyl]ethanol}, were synthesized. Crystallographic analysis reveals that polymer 1 exhibits a 2-D rhombohedral grid structure with (4, 4) nets, while polymer 2 has a 1-D double-chain framework. The structure of polymer 3 is similar to that of 1. We found that polymers 1–3 could effectively catalyze the oxidation of benzyl alcohol to benzaldehyde with H2O2 (30 mass-%) as oxidant in aqueous medium. Various reaction conditions were studied, and optimal reaction conditions were obtained. Under the optimal conditions, the selectivity to benzaldehyde was almost up to 100 % and the conversion of benzyl alcohol was 87 % for 1, 79 % for 2, and 68 % for 3. The results of the recycling test showed that the catalytic activity decreased by only about 7 % after three consecutive reaction cycles. However, under similar conditions, when we used the corresponding metal salt instead of the polymer as catalyst, or replaced the water with acetonitrile as solvent, neither the selectivity nor the conversion was the same. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)

Fe(Cu)‐Containing Coordination Polymers: Syntheses, Crystal Structures, and Applications as Benzyl Alcohol Oxidation Catalysts

Three novel ferrocenecarboxylato-bridged lanthanide dimers [Gd 2 (μ 2 -OOCFc) 2 (OOCFc) 4 (MeOH) 2 (H 2 O) 2 ].2MeOH. 2H 2 O (1) (Fc = (η 5 -C 5 H 5 )Fe(η 5 -C 5 H 4 )), [Nd 2 (μ 2 -OOCFc) 2 (OOCFc) 4 (H 2 O) 4 ].2MeOH.H 2 O (2), and [Y 2 (μ 2 -OOCFc) 2 -(OOCFc) 4 (H 2 O) 4 ].2MeOH (3) have been synthesized and characterized by single-crystal X-ray crystallography. In each complex, two Ln(III) (Ln = Gd, Nd, or Y) ions are bridged by two ferrocenecarboxylate anions as asymmetrically bridging ligands, leading to dimeric cores, [Ln 2 (μ 2 -OOCFc) 2 ]; each Ln(III) ion has an irregular polyhedral coordination environment with nine coordinated oxygen atoms derived from the ferrocenecarboxylate ligands and coordinated solvent molecules. In the solid-state structure of compound 1, [Gd 2 (μ 2 -OOCFc) 2 (OOCFc) 4 (MeOH) 2 (H 2 O) 2 ] groups are joined together by hydrogen bonds forming a two-dimensional network. Both compounds 2 and 3 show one-dimensional chain structures by hydrogen bonding; they are different from 1. Magnetic measurements show unexpected ferromagnetic coupling between the gadolinium(III) ions; the best fittings to the experimental magnetic susceptibilities gave J = 0.006 cm - 1 and g = 2.0 for 1. The magnetic behavior for 2 was also studied in the temperature range of 1.8-300 K.

Synthesis, crystal structures, and magnetic properties of three novel ferrocenecarboxylato-bridged lanthanide dimers.

A series of metal carboxylate complexes have been synthesized by treating 2,6-dicarboxamido-(2-pyridyl)-pyridine (H2dcapp), pyridine-2,5-dicarboxylate acid (2,5-H2pda), and phenanthroline (phen) wi...

From Dicarboxylic Acid to Tetranuclear Metallamacrocyclic Complex and 1D and 2D Polymers

Treatment of two kinds of ferrocenyl-substituted carboxylate ligands (3-ferrocenyl-2-crotonic acid, HOOC-CH=(CH(3))CFc (Fc=(eta(5)-C(5)H(5))Fe(eta(5)-C(5)H(4))) or O-ferrocecarbonyl benzoic acid, o-HOOCC(6)H(4)COFc with Pb(OAc)(2).3H(2)O, Zn(OAc)(2).2H(2)O, or Cd(OAc)(2).2H(2)O) resulted in four novel ferrocene-containing coordination polymers [[Pb(mu(2)-eta(2)-OOCCH=(CH(3))CFc)(2)].MeOH](n) (1), [[Zn(o-OOCC(6)H(4)COFc)(2)(4,4'-bipy)(H(2)O)(2)].2MeOH.2H(2)O](n) (4,4'-bipy = 4,4'-bipyridine) (2), [[Cd(o-OOCC(6)H(4)COFc)(2)(bpe)(MeOH)(2)].2H(2)O](n) (bpe = 1,2-bis(4-pyridyl)ethene) (3), and [Pb(o-OOCC(6)H(4)COFc)(eta(2)-o-OOCC(6)H(4)COFc)(bpe)](n)() (4). Their crystal structures have been characterized by single X-ray determinations. In polymer 1, Pb(II) ions are bridged by tridentate FcC(CH(3))=CHCOO(-) anions, forming an infinite chain [Pb(mu(2)-eta(2)-OOC=CH(CH(3))CFc)(2)](n). In polymers 2-4, there are three kinds of components, metal ions, o-FcCOC(6)H(4)COO(-) units, and organic bridging ligands. The bipyridine-based ligands connect metal ions leading to a one-dimensional chain with o-FcCOC(6)H(4)COO(-) units acting as monodentate or chelate ligands in the side chain. Such coordination polymers containing ferrocenyl-substituted carboxylate and bipyridine-based ligands are very rare. The solution-state differential pulse voltammetries of polymers 1-4 were determined. The results indicate that the half-wave potential of the ferrocenyl moieties is influenced by the Pb(II) ions in polymer 1 and strongly influenced by Zn(II), Cd(II), or Pb(II) ions in polymers 2-4. The thermal properties of the four polymers were also investigated.

Novel Pb(II), Zn(II), and Cd(II) coordination polymers constructed from ferrocenyl-substituted carboxylate and bipyridine-based ligands.

In this paper four metal–organic polymers {[Zn(fcz)Cl2]·CH3OH}n1, {[Cd(fcz)2Cl2]·CH3OH·2H2O}n2, {[Co(fcz)2Cl2]·2CH3OH}n3 and {[Cu(fcz)2Cl2]·2CH3OH}n4 (fcz = fluconazole: α-(2,4-difluorophenyl)-α-(1H-1,2,4-triazol-l-ylmethyl)-1H-1,2,4-triazole-l-ethanol) were synthesized and characterized by X-ray single crystal diffraction. Polymer 1 consists of 1-D infinite chains arranged along the b-axis. All of polymers 2–4 exhibit a 2-D rhombohedral grid structure. We study the third-order nonlinear optical properties of fcz and polymers 1–4 in DMF solution by using 8 ns laser pulses at 532 nm, and find that 1 and 4 exhibit different NLO properties from fcz and both 2 and 3 show similar NLO properties to fcz. 1 possesses strong NLO refractive effects and large NLO absorptive behaviors. 2, 3 and fcz exhibit strong refractive effects, but their NLO absorptive behaviors are weaker than that of 1. The NLO effects of 4 are very weak. The study of optical limiting (OL) effects by using 40 ps laser pulses at 532 nm shows that fcz and polymer 3 possess a strong OL effect. The optical limiting threshold values of 0.15 J cm−2 for fcz and 0.16 J cm−2 for 3 are comparable to those of many heterothiometallate clusters. Polymers 1, 2 and 4 show a weak OL effect. The fluorescent spectra in DMF solution (concentration: 1 × 10−4 mol dm−3) show that polymers 1–4 exhibit different luminescence properties from fcz. The maximum wavelength of polymers 1–3 are blue shifted gradually by 2–12 nm while polymer 4 exhibits a fluorescent self-quenching phenomenon. These results demonstrate that metal ions play an important part in the NLO and fluorescent properties of coordination polymers.

Yu Zhu

Papers

Fe(Cu)‐Containing Coordination Polymers: Syntheses, Crystal Structures, and Applications as Benzyl Alcohol Oxidation Catalysts

Synthesis, crystal structures, and magnetic properties of three novel ferrocenecarboxylato-bridged lanthanide dimers.

From Dicarboxylic Acid to Tetranuclear Metallamacrocyclic Complex and 1D and 2D Polymers

Novel Pb(II), Zn(II), and Cd(II) coordination polymers constructed from ferrocenyl-substituted carboxylate and bipyridine-based ligands.

A series of metal–organic polymers assembled from MCl2 (M = Zn, Cd, Co, Cu): structures, third-order nonlinear optical and fluorescent properties