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Issue 6, 2009
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Rigidity effect of the dithioether spacer on the size of the luminescent cluster (Cu2I2)n (n = 2, 3) in their coordination polymers

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Abstract

Treatment of CuI with the flexible PhS(CH2)4SPh dithioether ligand in MeCN solution affords the strongly luminescent metal–organic 2D coordination polymer [Cu4I4{μ-PhS(CH2)4SPh}2]n (1). The interpenetrated 2D network of 1 is built upon by Cu43-I)4 cubane-like clusters as secondary building units (SBUs), which are interconnected via bridging 1,4-bis(phenylthio)butane ligands. In contrast, the auto-assembly reaction of the unsaturated semi-flexible PhSCH2C[triple bond, length as m-dash]CCH2SPh ligand with CuI results in formation of the 3D metallopolymer [(Cu6I6){μ-PhSCH2C[triple bond, length as m-dash]CCH2SPh}3]n (2). The SBUs of luminescent 2 consist of discrete Cu63-I)6 hexagon prisms, which are coordinated with bridging 1,4-bis(phenythio)butyne ligands via Cu–S bonds. Contrary to the other rare literature-known examples of metallopolymers incorporating Cu6X6 SBUs as connecting nodes, the Cu⋯Cu interactions of 2 [2.8484(6) Å] are markedly shorter, being close to the sum of the Van der Waals radii of two Cu atoms (∼2.8 Å). The photophysics of these compounds, which exhibit reversible luminescence thermochromism, has been investigated in detail. The solid-state luminescence spectra of 1 and 2 feature at room temperature intense emissions around 560 and 555 nm, respectively. The luminescence properties of the unusual Cu63-I)6 hexagon prism motif are rationalized by means of DFT and TDDFT computations.

Graphical abstract: Rigidity effect of the dithioether spacer on the size of the luminescent cluster (Cu2I2)n (n = 2, 3) in their coordination polymers

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Publication details

The article was received on 29 Sep 2008, accepted on 30 Sep 2008 and first published on 15 Dec 2008


Article type: Paper
DOI: 10.1039/B816987J
Citation: Dalton Trans., 2009,0, 948-955
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    Rigidity effect of the dithioether spacer on the size of the luminescent cluster (Cu2I2)n (n = 2, 3) in their coordination polymers

    M. Knorr, F. Guyon, A. Khatyr, C. Däschlein, C. Strohmann, S. M. Aly, A. S. Abd-El-Aziz, D. Fortin and P. D. Harvey, Dalton Trans., 2009, 0, 948
    DOI: 10.1039/B816987J

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