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Role of hydrogen bonds in molecular packing of photoreactive crystals: templating photodimerization of protonated stilbazoles in crystalline state with a combination of water molecules and chloride ions

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Abstract

A difference in photobehavior and molecular packing between hydrated and anhydrous crystals of protonated trans-stilbazoles has been identified. While stilbazoles are not photoreactive in the crystalline state, upon protonation with HCl in the solid state they dimerized to a single dimer (anti-head-tait) when exposed to UV light. In these photoreactive crystals the protonated stilbazole molecules are arranged in a ladder-like format with the rungs made up of water molecules and chloride ions. A combination of water and chloride ion holds the protonated trans-stilbazoles through either N-H … O or N-H…Cl− interactions. Anhydrous protonated stilbazole crystals prepared by heating the ’wet’ crystals under reduced pressure were inert upon exposure to UV light. As per X-ray crystal structure analyses these light stable crystals did not contain water molecules in their lattice. The current investigation has established that water molecules are essential for photodimerization of crystalline protonated trans-stilbazoles. To compare the reactivity of protonated trans-stilbazoles with that of protonated c/s-stilbazoles, photoreactivity and packing arrangement of cis-4-iodo stilbazole·HCl salt was examined. This molecule in the crystalline state only isomerized to the trans isomer and did not dimerize. Thus, while the trans isomer dimerized and did not isomerize, the cis isomer only isomerized and did not dimerize in the crystalline state. To probe the role of cation…π interaction in the packing of protonated trans-stilbazoles, energies of various types of packing in the gas phase were estimated by MP-2 calculations and cation…π interaction was found to be unimportant in the packing of protonated trans-stilbazole crystals investigated here.

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  1. Department of Chemistry, University of Miami, Coral Gables, FL, 33146, USA

    Barnali Mondal, Tingting Zhang, Rajeev Prabhakar, Burjor Captain & V. Ramamurthy

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Correspondence to Burjor Captain.

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Electronic supplementary information (ESI) available: All crystallographic data (CIF files) of published structures of seven reactive stilbazole-HCl salts (1–5, 7 and 8) have been deposited previously with CCDC and their numbers are 813287-818801. Structures of unreactive trans crystals and the cis crystals have been solved and their CIF files are deposited. CCDC 1008122-1008125. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/ C4pp00221k

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Mondal, B., Zhang, T., Prabhakar, R. et al. Role of hydrogen bonds in molecular packing of photoreactive crystals: templating photodimerization of protonated stilbazoles in crystalline state with a combination of water molecules and chloride ions. Photochem Photobiol Sci 13, 1509–1520 (2014). https://doi.org/10.1039/c4pp00221k

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