Please use this identifier to cite or link to this item: https://doi.org/10.1002/chem.201103791
Title: Thermal cleavage of cyclobutane rings in photodimerized coordination-polymeric sheets
Authors: Chanthapally, A.
Kole, G.K.
Qian, K.
Tan, G.K.
Gao, S.
Vittal, J.J. 
Keywords: Cycloaddition
Dimerization
Magnetic properties
Photochemistry
Polymers
Issue Date: 18-Jun-2012
Source: Chanthapally, A., Kole, G.K., Qian, K., Tan, G.K., Gao, S., Vittal, J.J. (2012-06-18). Thermal cleavage of cyclobutane rings in photodimerized coordination-polymeric sheets. Chemistry - A European Journal 18 (25) : 7869-7877. ScholarBank@NUS Repository. https://doi.org/10.1002/chem.201103791
Abstract: Three coordination polymers, [Cd 2achtungtrenung(pvba) 2achtungtrenung(tbdc)achtungtrenung(dmf) 2] (1), [co 2-achtungtrenung(pvba) 2achtungtrenung(tbdc) achtungtrenung(dmf) 2achtungtrenung(h 2o) 2] (2), and [ni 2achtungtrenung(pvba)2achtungtrenung(tbdc)achtungtrenung(dmf) 2achtungtrenung(H 2O) 2] (3) (H 2tbdc=2,3,5,6-tetrabromobenzenedicarboxylic acid, Hpvba=trans-2-(4'-pyridyl)vinylbenzoic acid), were synthesized by solvothermal methods. The solid-state structures of compounds 1 and 2 were determined by X-ray crystallography. In compounds 1 and 2, the bimetallic cores acted as secondary building units that connected the tbdc ligands in one direction and a pair of pvba ligands, which were aligned in a head-to-tail parallel manner, in the orthogonal direction to form sheet structures. The C=C bonds in these pvba ligand pairs in all three compounds were well-aligned to undergo quantitative [2+2] cycloaddition reactions in the solid state under UV irradiation, thereby yielding their cyclobutane derivatives. This photochemical reaction appeared to facilitate structural transformations from one 2D structure into another in the solid state. The photoreactive CoII-and N iII coordination polymers exhibited a reversible dehydration-rehydration reaction that was accompanied by color changes from pink to purple and green to yellow, respectively, owing to a change in coordination number from six to five. Magnetic studies showed that compound 2 was an antiferromagnet, which displayed a field-dependent transition with a critical field (H c) of 40 kOe at 2 K; the antiferromagnetic interaction between the Co 2 units was strengthened and weakened by dehydration and UV irradiation, respectively. The cyclobutane ligand in the photodimerized products was cleaved on heating to yield a mixture of trans-and cis-isomers of pvba, as monitored by 1H NMR spectroscopy. The Cd II coordination polymer underwent quantitative cleavage of the cyclobutane ring whilst the other two underwent partial cleavage. © 2012 Wiley-VCH Verlag GmbH&Co. KGaA, Weinheim.
Source Title: Chemistry - A European Journal
URI: http://scholarbank.nus.edu.sg/handle/10635/95283
ISSN: 09476539
DOI: 10.1002/chem.201103791
Appears in Collections:Staff Publications

Show full item record
Files in This Item:
There are no files associated with this item.

SCOPUSTM   
Citations

29
checked on Feb 15, 2018

WEB OF SCIENCETM
Citations

31
checked on Jan 30, 2018

Page view(s)

21
checked on Feb 19, 2018

Google ScholarTM

Check

Altmetric


Items in DSpace are protected by copyright, with all rights reserved, unless otherwise indicated.