The chemistry of the coordination polymers has in recent years advanced extensively, affording various architectures, which are constructed from a variety of molecular building blocks with different interactions between them. The next challenge is the chemical and physical functionalization of these architectures, through the porous properties of the frameworks. This review concentrates on three aspects of coordination polymers: 1). the use of crystal engineering to construct porous frameworks from connectors and linkers ("nanospace engineering"), 2). characterizing and cataloging the porous properties by functions for storage, exchange, separation, etc., and 3). the next generation of porous functions based on dynamic crystal transformations caused by guest molecules or physical stimuli. Our aim is to present the state of the art chemistry and physics of and in the micropores of porous coordination polymers.

Functional porous coordination polymers.

Die Chemie der Koordinationspolymere hat sich in den vergangenen Jahren rasant entwickelt. Strukturen aus einer Vielzahl molekularer Bausteine mit unterschiedlichen Wechselwirkungen sind mittlerweile zuganglich. Die nachste Stufe ist die chemische und physikalische Funktionalisierung dieser Architekturen durch Einstellung ihrer Porositaten. Dieser Aufsatz konzentriert sich auf drei Aspekte von Koordinationspolymeren: 1) Anwendung von Kristall-Engineering zum Aufbau poroser Geruste aus Konnektoren und Linkern (“Nanospace-Engineering”), 2) Charakterisierung und Katalogisierung poros-struktureller Funktionalitat fur Anwendungen in Speicherungs-, Austausch-, Trennprozessen etc. und 3) poros-strukturelle Funktionalitat auf der Basis dynamischer Kristallumwandlungen durch Gastmolekule oder physikalische Reize. Ziel ist es, den aktuellen Stand der Forschung zur Chemie und Physik von und in den Mikroporen poroser Koordinationspolymere vorzustellen.

Funktionale poröse Koordinationspolymere

Structure and Bonding in Copper(I) Carbonyl and Cyanide Complexes

Four complexes of CuCN with imidazoles have been prepared by adding the ligand to a solution of CuCN in aqueous sodium thiosulfate. The imidazole ligands used were 2-methylimidazole (mim), 1,2-dimethylimidazole (dmim), 5-chloro-1-methylimidazole (clmim), and 2-phenylimidazole (phim). Complex 1, (CuCN)(mim) is monoclinic, C2/c, a = 9.565(3), b = 7.764(5), c = 8.983(8) A, β = 96.76(3)°, Z, = 4, Complex 2, (CuCN)(dmim) is monoclinic, P21/c, a = 8.120(2), b = 11.796(4), c = 16.375(9) A, β, = 100.87(4)°, Z = 8. Complex 3, (CuCN) (clmim) is monoclinic, C2/c, a = 24.907(4), b = 6.894(5), c = 18.259(4) A, β = 102.79(2)°, Z = 16. Complex 4, (CuCN)(phim) is orthorhombic, Pca21, a = 9.204(4), b = 8.125(2), c = 26.304(6) A, Z, = 8. Complexes 1, 2, and 4 have one-dimensional chains –Cu–CN–Cu– with an imidazole bonded to each Cu. Complex 3 has a two-dimensional sheet of CuCN, again with an imidazole bonded to each Cu. In 1 the imidazole group is disordered by a two-fold rotation approximately around the N···N direction in the imidazole group. In 3 one of the imidazole groups has a disorder involving exchange of the Cl and CH3.

Crystal structures of four complexes produced by reaction of copper(I) cyanide with imidazoles

A new nanosized host-guest supramolecular coordination polymer based on copper cyanide network and 1,7-diaminoheptane: Comparative structure study and catalytic activity

In the polymeric 3/1 complex of copper(I) cyanide and thiomorpholine, 3CuCN.C 4 H 9 NS or [Cu 3 (CN) 3 (C 4 H 9 -NS)] n , the CuCN forms two-dimensional sheets, which are held together by the thiomorpholine. Each thiomorpholine molecule bonds to three different sheets.

http://journals.iucr.org/c/issues/1999/12/00/bk1494/bk1494.pdf

Copper(I) cyanide-thiomorpholine (3/1)

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Copper(I) cyanide-thiomorpholine (3/1)