Abstract
A 2D hydrogen-bonded dinuclear Zn(II) complex, [{Zn(H2O)3(bpe)2}2(bpe)](NO3)4⋅3bpe ⋅14H2O, 1 (bpe = 4,4′-bipyridylethylene) containing coordination complex cations, [{Zn(H2O)3(bpe)2}2(μ-bpe)] 4+ and free bpe and lattice water molecules shows face-to-face, π⋯π stacking of two of the four free bpe molecules with coordinated bpe ligands. Out of eight bpe molecules, six are aligned in parallel fashion with short C ⋯C distances of 3.663–3.814 Å and they undergo photochemical [2 + 2] cycloaddition reaction. The photoreaction conducted on ground sample of 1 in the solid-state affords rctt-tetrakis(4-pyridyl)cyclobutane (rctt-tpcb) product in 75% yield. The molecular movement of free bpe molecules was tested by conducting the photoreaction in ground sample and heated sample of single crystals. The photoreactivity study of 1 indicates that the free bpe molecules are locked between the cationic [{Zn(H2O)3(bpe)2}2(bpe)] 4+ layers.
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Acknowledgments
The author would like to acknowledge the support provided by the Deanship of Scientific Research (DSR) at King Fahd University of Petroleum & Minerals (KFUPM) for funding this work through project No. IN131005. The author is grateful to Prof. Jagadese J. Vittal, National University of Singapore for helpful discussion on the manuscript.
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All additional information pertaining to the characterization of photoreacted 1 under various conditions using 1H NMR, product distribution, TGA, and crystallographic data of 1 are given in the Supporting Information available at www.ias.ac.in/chemsci.
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PEEDIKAKKAL, A.M.P. Solid-state Photochemical [2+2] Cycloaddition Reaction of Hydrogen-Bonded Zn(II) Metal Complex Containing Several Parallel C=C Bonds. J Chem Sci 129, 239–247 (2017). https://doi.org/10.1007/s12039-016-1218-6
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DOI: https://doi.org/10.1007/s12039-016-1218-6