Rigidity effect of the dithioether spacer on the ...

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Title Rigidity effect of the dithioether spacer on the size of the luminescent cluster (Cu(2)I(2))(n) (n = 2, 3) in their coordination polymers
Author(s) Michael Knorr, Fabrice Guyon, Abderrahim Khatyr, Christian Daschlein, Carsten Strohmann, Shawkat M. Aly, Alaa S. Abd-El-Aziz, Daniel Fortin, Pierre D. Harvey
Journal Dalton Transactions (Cambridge, England : 2003)
Date 2009
Volume
Issue 6
Start page 948
End page 955
Abstract Treatment of CuI with the flexible PhS(CH(2))(4)SPh dithioether ligand in MeCN solution affords the strongly luminescent metal-organic 2D coordination polymer [Cu(4)I(4){mu-PhS(CH(2))(4)SPh}(2)](n) (). The interpenetrated 2D network of is built upon by Cu(4)(mu(3)-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 PhSCH(2)C[triple bond, length as m-dash]CCH(2)SPh ligand with CuI results in formation of the 3D metallopolymer [(Cu(6)I(6)){mu-PhSCH(2)C[triple bond, length as m-dash]CCH(2)SPh}(3)](n) (). The SBUs of luminescent consist of discrete Cu(6)(mu(3)-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 Cu(6)X(6) SBUs as connecting nodes, the CuCu interactions of [2.8484(6) A] are markedly shorter, being close to the sum of the Van der Waals radii of two Cu atoms ( approximately 2.8 A). The photophysics of these compounds, which exhibit reversible luminescence thermochromism, has been investigated in detail. The solid-state luminescence spectra of and feature at room temperature intense emissions around 560 and 555 nm, respectively. The luminescence properties of the unusual Cu(6)(mu(3)-I)(6) hexagon prism motif are rationalized by means of DFT and TDDFT computations.
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