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Synthesis, Spectroscopy, Luminescence and Structures of Trinuclear and Hexanuclear CuI Clusters with 2,4,6-Trimercaptotriazine

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Abstract

Copper cluster chemistry with a multifunctional 2,4,6-trimercaptotriazine thio-ligand in the presence of triphenylphosphine as a co-ligand is investigated. In a typical case, a reaction of copper(I) chloride with 2,4,6-trimercaptotriazine (tmtH3) in a mixture of acetonitrile–methanol at room temperature, followed by the addition of solid Ph3P (1:1:2 molar ratio) yielded a yellow compound of composition, [Cu3Cl2(tmtH2)(PPh3)6] 1. However, this reaction when performed in dimethyl formamide (DMF) in the presence of Et3N Lewis base (Cu:tmtH3:PPh3::1:1:2 molar ratio) yielded yellow crystals of hexa-nuclear cluster, [Cu6(tmt)2(PPh3)6].(DMF)2 2. A single crystal x-ray crystallography revealed that in tri-nuclear cluster 1, all three sulfur donor atoms are bonded to three CuI ions, resulting in the two four coordinated Cu(S,Cl,P2) and one Cu(N,S,P2) cores. As regards hexa-nuclear cluster 2, each Cu is bonded to one N, one S and one P donor atom, generating six Cu(N,S,P) coordination cores, and each Cu has a distorted trigonal planar geometry. Two parallel triazine rings are held in a close proximity of 3.063 Å by six Cu–S bridges. Spectroscopic, luminescence and versatility of bonding modes are described. The tri-nuclear cluster, with a new coordination mode of (tmtH2), represents a rare example in copper-heterocyclic-2-thione chemistry.

Graphic Abstract

Copper(I) chloride with tmtH3 in acetonitrile–methanol mixture has afforded a novel trinuclear luminescent cluster.

Reaction of copper(I) chloride with 2,4,6-trimercaptotriazine and PPh3 in CH3CN–CH3OH mixture yielded a trinuclear luminescent cluster of composition, [Cu3Cl2(tmtH2)(PPh3)6].

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Funding

Financial assistance from University Grants Commission (UGC) Major Project F. No. 34-307/2008 (SR), under UGC(BSR) scheme and the Council of Scientific and Industrial Research (CSIR), New Delhi, for Emeritus Grant [21(0904)/12-EMR-II] to Tarlok Singh Lobana, New Delhi are gratefully acknowledged.

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Correspondence to Tarlok Singh Lobana.

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Lobana, T.S., Sandhu, A.K., Hundal, G. et al. Synthesis, Spectroscopy, Luminescence and Structures of Trinuclear and Hexanuclear CuI Clusters with 2,4,6-Trimercaptotriazine. J Chem Crystallogr 52, 409–421 (2022). https://doi.org/10.1007/s10870-021-00897-y

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  • DOI: https://doi.org/10.1007/s10870-021-00897-y

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