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 (Cu2I2)n (n = 2, 3) in their coordination polymers. |
| Author(s) | M. Knorr, F. Guyon, A. Khatyr, C. Daeschlein, C. Strohmann, S. Aly, A. Abd-El-Aziz, D. Fortin, P. Harvey |
| Journal | Section Title: Inorganic Chemicals and Reactions, Dalton Transactions |
| Date | 2009 |
| Volume | |
| Issue | 6 |
| Start page | 948 |
| End page | 955 |
| Abstract | Treatment of CuI with the flexible PhS(CH2)4SPh dithioether ligand in MeCN soln. affords the strongly luminescent metal-org. 2D coordination polymer [Cu4I4{μ-PhS(CH2)4SPh}2]n (1). The interpenetrated 2D network of 1 is built upon by Cu4(μ3-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 unsatd. semi-flexible PhSCH2C≡CCH2SPh ligand with CuI results in formation of the 3D metallopolymer [(Cu6I6){μ-PhSCH2C≡CCH2SPh}3]n (2). The SBUs of luminescent 2 consist of discrete Cu6(μ3-I)6 hexagon prisms, which are coordinated with bridging 1,4-bis(phenylthio)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 compds., which exhibit reversible luminescence thermochromism, has been investigated in detail. The solid-state luminescence spectra of 1 and 2 feature at room temp. intense emissions around 560 and 555 nm, resp. The luminescence properties of the unusual Cu6(μ3-I)6 hexagon prism motif are rationalized by means of DFT and TDDFT computations. [on SciFinder(R)] |
| DOI | 10.1039/b816987j |
| ISSN | 1477-9226 |
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