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Issue 45, 2013
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Coordination polymers of a dipyridylazacrown ligand: structural, thermal and spectroscopic properties

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Abstract

Treatment of the dipyridylazacrown ether ligand N,N′-bis(4-pyridyl-methyl)diaza-18-crown-6 (bpmdc), with hydrated transition metal perchlorate salts resulted in 2D networks with the composition [M(H2O)2(Hbpmdc)2](ClO4)4·xH2O (M2+ = Ni, x = 4 (1); Cu, x = 2 (2) and Zn, x = 4 (3)). The addition of sodium thiocyanate led to displacement of the aqua ligands, yielding [M(NCS)2(Hbpmdc)2](ClO4)2·2H2O (M2+ = Fe (4), Ni (5)), as well as a THF containing variant of Fe (6). A five-coordinate, copper-containing 2D network, [Cu(NCS)(bpmdc)2](NCS) (7), was isolated in the case of copper, while zinc proved to be the exception to the 2D coordination polymer motif, yielding a 1D chain motif [Zn(NCS)2(bpmdc)2] (8). Across these structures the dipyridylazacrown ether ligand showed a remarkably consistent adoption of the S-configuration when empty or singly protonated with a water guest, with bridging lengths varying by only 1.3 Å. The magnetic behaviour of the Fe2+ network 4 was investigated and the d6 compound was found to remain high spin at all temperatures between 300 and 2 K, and thus did not show spin-crossover behaviour.

Graphical abstract: Coordination polymers of a dipyridylazacrown ligand: structural, thermal and spectroscopic properties

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Article information


Submitted
21 Jun 2013
Accepted
12 Aug 2013
First published
13 Aug 2013

CrystEngComm, 2013,15, 9655-9662
Article type
Paper

Coordination polymers of a dipyridylazacrown ligand: structural, thermal and spectroscopic properties

W. J. Gee, B. Moubaraki, K. S. Murray and S. R. Batten, CrystEngComm, 2013, 15, 9655
DOI: 10.1039/C3CE41202D

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