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 purpose of this critical review is to give a representative and comprehensive overview of the arising developments in the field of magnetic metal–organic frameworks, in particular those containing cobalt(II). We examine the diversity of magnetic exchange interactions between nearest-neighbour moment carriers, covering from dimers to oligomers and discuss their implications in infinite chains, layers and networks, having a variety of topologies. We progress to the different forms of short-range magnetic ordering, giving rise to single-molecule-magnets and single-chain-magnets, to long-range ordering of two- and three-dimensional networks (323 references).

Magnetic metal-organic frameworks.

Polycatenation, polythreading and polyknotting in coordination network chemistry

: 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

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

A staggered arrangement like that of the hydrogen atoms in ethane is exhibited by the six phenol groups about each pair of silver atoms in the self-assembled three-dimensional coordination networks [Ag(2)(H(2)L)(3)](n)X(2n) (H(2)L=N,N'-bis(salicylidene)-1,4-diaminobutane; X(-)=NO(3)(-) or ClO(4)(-)); the former is depicted (for clarity the H(2)L ligands are represented by long rods and the Ag atoms by hatched circles). These solids contain short ligand-unsupported metal-metal bonds and display intense blue photoluminescence at room temperature.

Self-Assembled Three-Dimensional Coordination Polymers with Unusual Ligand-Unsupported Ag-Ag Bonds: Syntheses, Structures, and Luminescent Properties.

Four mixed-ligand complexes of [M(mpa)(phen)]n [M =C d (1 )o r Zn (2) and mpa = m-phthalate and phen = 1,10-phenanthroline) and [M2(mpa)2(2,2-bpy)2]n [M = Zn (3 )o r Cd (4) and 2,2-bpy = 2,2-bipyridine] have been synthesized and their crystal structures have been established by single-crystal X-ray diffraction. They all consist of one-dimensional ribbons featuring dinuclear units. Both 1 and 2 crystallize isomorphously in the monoclinic space group P2/c and feature

Helical Ribbons of Cadmium(II) and Zinc(II) Dicarboxylates with Bipyridyl- Like Chelates Syntheses, Crystal Structures and Photoluminescence

Imidazo[4,5-f]1,10-phenanthroline (ip),
2-phenylimidazo[4,5-f][1,10]phenanthroline (pip) and
their (bipy)
 2
Ru
 2+
 complexes
(bipy = 2,2′-bipyridine) have been synthesized and
characterized The oxidation potentials of
[Ru(bipy)
 2
(ip)]
 2+
 and
[Ru(bipy)
 2
(pip)]
 2+
 were found to be 1254 and
1284 V vs saturated calomel electrode respectively; the
reduction of ip and pip appears to be irreversible at ca
-085 V The photophysical properties of the complexes were
perturbed in the presence of calf thymus DNA The distinct changes
including hypo- or hyper-chromicity at different UV/VIS absorption
bands, enhancements of integrated emission intensity and excited-state
lifetime, and efficiency of emission quenching by
[Fe(CN)
 6
]
 4-
 all indicate the stronger
binding affinity to DNA of [Ru(bipy)
 2
(pip)]
 2+
 over
that of [Ru(bipy)
 2
(ip)]
 2+
, consistent with the
greater planar area and extended π system of the pip ligand The
luminescence of the complexes showed monoexponential decay at any
[DNA]∶[Ru] ratio The circular dichroism signals of the dialysates
of the racemic complexes against calf thymus DNA suggest that the
complexes bind to the DNA with enantioselectivity favouring the Δ
isomers These phenomena all suggest that the complexes bind through
intercalation of ip or pip into base pairs The crystal structure of
[Ru(bipy)
 2
(ip)][ClO
 4
]
 2
·H
 2

O was determined; it contains the planar bidentate ligand ip and
two twisted bipy ligands with torsional angles between each bipyridine
ring pair of 57 and 86°

http://nathan.instras.com/MyDocsDB/doc-531.pdf

Bis(2,2′-bipyridine)ruthenium(II)complexes withimidazo[4,5-f ][1,10]-phenanthroline or2-phenylimidazo[4,5-f ][1,10]phenanthroline

A new copper(II) fluorescent sensor 5,10,15,20-tetra((p-N,N-bis(2-pyridyl)amino)phenyl)porphyrin zinc (1) has been designed and synthesized by the Ullmann-type condensation of bromoporphyrin zinc with 2,2‘-dipyridylamine (dpa) under copper powder as a catalyst as well as with K2CO3 as the base in a DMF solution. It consists of two separately functional moieties:  the zinc porphyrin performs as a fluorophore, and the dpa-linked-to-zinc porphyrin acts as a selected binding site for metal ions. It displays a high selectivity and antidisturbance for the Cu2+ ion among the metal ions examined (Na+, Mg2+, Cr3+, Mn2+, Fe2+, Co2+, Ni2+, Cu2+, Ag+, Zn2+, Cd2+, Hg2+, and Fe3+) and exhibits fluorescence quenching upon the binding of the Cu2+ ion with an “on−off”-type fluoroionophoric switching property. The detection limit is found to be 3.3 × 10-7 M (3s blank) for Cu2+ ion in methanol solution, and its fluorescence can be revived by the addition of EDTA disodium solution. The design strategy and remarkable photophy...

Bao-Hui Ye

Papers

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

Self-Assembled Three-Dimensional Coordination Polymers with Unusual Ligand-Unsupported Ag-Ag Bonds: Syntheses, Structures, and Luminescent Properties.

Helical Ribbons of Cadmium(II) and Zinc(II) Dicarboxylates with Bipyridyl- Like Chelates Syntheses, Crystal Structures and Photoluminescence

Bis(2,2′-bipyridine)ruthenium(II)complexes withimidazo[4,5-f ][1,10]-phenanthroline or2-phenylimidazo[4,5-f ][1,10]phenanthroline

A copper(II) ion-selective on-off-type fluoroionophore based on zinc porphyrin-dipyridylamino.