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) | M. Knorr, F. Guyon, A. Khatyr, C. Daschlein, C. Strohmann, S. Aly, A. Abd-El-Aziz, D. Fortin, P. 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. |
| ISSN | 1477-9226 |
| Use/Reproduction | Contact Publisher |
| Text | http://www.islandscholar.ca/scholartest/download_ds/ir:1607/PDF |
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