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Cooperative metal–ligand influence on the formation of coordination polymers, and conducting and photophysical properties of Tl(i) β-oxodithioester complexes

Yadav, C. L., Rajput, G., Manar, K. K., Kumari, K., Drew, M. G. B. and Singh, N. (2018) Cooperative metal–ligand influence on the formation of coordination polymers, and conducting and photophysical properties of Tl(i) β-oxodithioester complexes. Dalton Transactions, 47 (45). pp. 16264-16278. ISSN 1477-9234

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To link to this item DOI: 10.1039/c8dt03694b


Eight novel Tl(I) β-oxodithioester complexes, [TlL]n (1–8), with ligands, L = methyl-3-hydroxy-3-(2-furyl)-2-propenedithioate (L1), methyl-3-hydroxy-3-(2-thienyl)-2-propenedithioate (L2), methyl-3-hydroxy-3-(3-pyridyl)-2-propenedithioate (L3), methyl-3-hydroxy-3-(4-pyridyl)-2-propenedithioate (L4), methyl-3-hydroxy-3-(9-anthracenyl)-2-propenedithioate (L5), methyl-3-hydroxy-3-(4-fluorophenyl)-2-propenedithioate (L6), methyl-3-hydroxy-3-(4-chlorophenyl)-2-propenedithioate (L7) and methyl-3-hydroxy-3-(4-bromophenyl)-2-propenedithioate (L8), were synthesized and thoroughly characterized by elemental analysis, and IR, UV-Vis, 1H and 13C{1H} NMR spectroscopy, and their structures were ascertained by X-ray crystallography. Complexes 1 and 2 crystallized in P21 and P212121 chiral space groups, respectively, and were studied using Circular Dichroism (CD) spectra. Solid state structural analyses revealed that the β-oxodithioester ligands are bonded to Tl(I) ions in (O, S) chelating and chelating–bridging modes, thereby forming different types of 1D and 2D coordination polymeric structures. By considering the metal-assisted bonding interactions, various coordination numbers of 5–8 and 10 are established around the metal centre. Except for 5 and 7a which have Tl⋯Tl separations at 3.724(1) and 3.767(1), 3.891(1) Å respectively, the remaining complexes have no Tl⋯Tl distances <4.0 Å. This indicates that the majority of structures contain only weak inter- and intramolecular thallophilic interactions. The structures of 1–8 highlight the role played by variations in substituents in the dithioester unit in the structure and properties of the complexes. The multi-dimensional assembly in these complexes rests on important non-covalent C–H⋯π (TlOSC3, chelate), C–H⋯X (X = F, Cl, O, N), C–H⋯π, H⋯H and rare Tl⋯H–C intermolecular anagostic interactions. The Tl⋯H–C anagostic interactions together with C–O⋯Tl and C–S⋯Tl interactions formed 7-, 11- and 12-membered chelate rings about the metal centers. The anagostic interactions in 1, 2 and 7b were assessed by theoretical calculations. All the complexes showed bright green luminescent emissions in solution and solid phases. Time-resolved emission spectra revealed a triexponential decay curve and short mean lifetime for fluorescence behavior.

Item Type:Article
Divisions:Life Sciences > School of Chemistry, Food and Pharmacy > Department of Chemistry
ID Code:80640
Publisher:Royal Society of Chemistry

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