Hydrogen bonded networks based on hexarhenium(III) chalcocyanide cluster complexes structural and photophysical characterization

Alexandra Ledneva (1) , Sylvie Ferlay (2) , Nikolay G. Naumov (3, 1) , Matteo Mauro (2) , Stéphane Cordier (4) , Nathalie Kyritsakas (2) , Mir Wais Hosseini (2)

1 NIC - Nikolaev Institute of Inorganic Chemistry [Novosibirsk]
2 CMC - Chimie de la matière complexe
3 NSU - Novosibirsk State University
4 ISCR - Institut des Sciences Chimiques de Rennes

Two series of isostructural compounds resulting from the combination of the four-fold hydrogen bond donors bisamidinium cations, namely 1-2H(+) and 2-2H(+), and the anionic chalcocyanide clusters of general formula [Re(6)Qi8(CN)a6](4-) are presented (Q = S or Se; where i and a denote inner and apical position, respectively). 1-2H(+) is built upon two imidazolium groups linked together by a -(CH2)(2)- alkyl chain. 2-2H(+) is built upon two hydroxyamidinium groups linked together via a phenyl group and, in consequence, it exhibits a planar geometry. This ionic association leads to either two or three-dimensional hydrogen-bonded networks in the solid state, as confirmed by X-ray crystallographic analysis. The solid-state structures arise from the recognition between the pendant C[triple bond]N ligands of the cluster cores and the amidinium H-bond donors. The luminescence properties of the compounds are investigated in the solid state by means of steady-state and time-resolved techniques. Results are discussed and compared with those measured for the parent Cs-4[Re(6)Si8(CN)a6] and Cs-4[Re(6)Sei8(CN)a6] species. The H-bonded networks display featureless deep-red emission bands centered at (em) = 722 and 737 nm and average excited-state lifetimes ranging between 11.5 and 14.8 s, in accordance with the triplet nature of the radiative process. These photoluminescence properties are similar to the Cs+ homologues and are attributed to the [Re(6)Qi8](2+) emitting core.

Domains: Chemical Sciences; Coordination chemistry; Chemical Sciences

Alexandra Ledneva, Sylvie Ferlay, Nikolay G. Naumov, Matteo Mauro, Stéphane Cordier, et al.. Hydrogen bonded networks based on hexarhenium(III) chalcocyanide cluster complexes structural and photophysical characterization. New Journal of Chemistry, 2018, 42 (14), pp.11888-11895. ⟨10.1039/c8nj02310g⟩. ⟨hal-01861410⟩