TY - JOUR

T1 - Hydrogen bonded networks based on hexarhenium(III) chalcocyanide cluster complexes

T2 - structural and photophysical characterization

AU - Ledneva, Alexandra

AU - Ferlay, Sylvie

AU - Naumov, Nikolay G.

AU - Mauro, Matteo

AU - Cordier, Stéphane

AU - Kyritsakas, Nathalie

AU - Hosseini, Mir Wais

N1 - Publisher Copyright: © The Royal Society of Chemistry and the Centre National de la Recherche Scientifique 2018.

PY - 2018/7/21

Y1 - 2018/7/21

N2 - 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 [Re6Qi8(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-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 Cs4[Re6Si8(CN)a6] and Cs4[Re6Sei8(CN)a6] species. The H-bonded networks display featureless deep-red emission bands centered at λem = 722 and 737 nm and average excited-state lifetimes ranging between 11.5 and 14.8 μs, in accordance with the triplet nature of the radiative process. These photoluminescence properties are similar to the Cs+ homologues and are attributed to the [Re6Qi8]2+ emitting core.

AB - 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 [Re6Qi8(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-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 Cs4[Re6Si8(CN)a6] and Cs4[Re6Sei8(CN)a6] species. The H-bonded networks display featureless deep-red emission bands centered at λem = 722 and 737 nm and average excited-state lifetimes ranging between 11.5 and 14.8 μs, in accordance with the triplet nature of the radiative process. These photoluminescence properties are similar to the Cs+ homologues and are attributed to the [Re6Qi8]2+ emitting core.

KW - OCTAHEDRAL RHENIUM CLUSTER

KW - SENSITIZED SOLAR-CELLS

KW - PRUSSIAN BLUE ANALOGS

KW - CRYSTAL-STRUCTURES

KW - EXCITED-STATE

KW - MOLECULAR TECTONICS

KW - SELENIDE CLUSTERS

KW - SOLID-STATE

KW - LIGANDS

KW - LUMINESCENT

UR - http://www.scopus.com/inward/record.url?scp=85049734328&partnerID=8YFLogxK

U2 - 10.1039/C8NJ02310G

DO - 10.1039/C8NJ02310G

M3 - Article

AN - SCOPUS:85049734328

VL - 42

SP - 11888

EP - 11895

JO - New Journal of Chemistry

JF - New Journal of Chemistry

SN - 1144-0546

IS - 14

ER -