Solid‐State Structural Transformations and Photoreactivity of 1D‐Ladder Coordination Polymers of PbII |
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| Authors: | Dr. Goutam Kumar Kole Dr. Abdul Malik Puthan Peedikakkal Belinda Mei Fang Toh Prof. Dr. Jagadese J. Vittal |
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| Affiliation: | Department of Chemistry, National University of Singapore, Science Drive 3, 117543 (Singapore), Fax: (+65)?67791691 |
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| Abstract: | An attempt has been made to design double‐stranded ladder‐like coordination polymers (CPs) of hemidirected PbII. Four CPs, [Pb(μ‐bpe)(O2C‐C6H5)2] ? 2H2O ( 1 ), [Pb2(μ‐bpe)2(μ‐O2C‐C6H5)2(O2C‐C6H5)2] ( 2 ), [Pb2(μ‐bpe)2(μ‐O2C‐p‐Tol)2(O2C‐p‐Tol)2] ? 1.5 H2O ( 3 ) and [Pb2(μ‐bpe)2(μ‐O2C‐m‐Tol)2(O2C‐m‐Tol)2] ( 4 ) (bpe=1,2‐bis(4′‐pyridyl)ethylene), have been synthesised and investigated for their solid‐state photoreactivity. CPs 2 – 4 , having a parallel orientation of bpe molecules in their ladder structures and being bridged by carboxylates, were found to be photoreactive, whereas CP 1 is a linear one‐dimensional (1D) CP with guest water molecules aggregating to form a hydrogen‐bonded 1D structure. The linear strands of 1 were found to pair up upon eliminating lattice water molecules by heating, which led to the solid‐state structural transformation of photostable linear 1D CP 1 into photoreactive ladder CP 2 . In the construction of the double‐stranded ladder‐like structures, the parallel alignment of C?C bonds in 2 – 4 is dictated by the chelating and μ2‐η2:η1 bridging modes of the benzoate and toluate ligands. The role of solvents in the formation of such double‐stranded ladder‐like structures has also been investigated. A single‐crystal‐to‐single‐crystal transformation occurred when 4 was irradiated under UV light to form [Pb2(rctt‐tpcb)(μ‐O2C‐m‐Tol)2(O2C‐m‐Tol)2] ( 5 ). |
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| Keywords: | coordination polymers cycloaddition lead photochemistry solid‐state reactions structure elucidation |
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