期刊
DALTON TRANSACTIONS
卷 41, 期 18, 页码 5486-5496出版社
ROYAL SOC CHEMISTRY
DOI: 10.1039/c2dt12398c
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资金
- South African National Research Foundation
- University of KwaZulu-Natal
- Department of Labour
Treatment of [Pt{4'-(Ph)trpy}Cl]SbF6 with AgSCN in a metathesis reaction in refluxing acetonitrile affords, after work-up, single crystals of [Pt{4'-(Ph) trpy}(NCS)]SbF6 center dot CH3CN, where trpy is 2,2': 6', 2 ''-terpyridine. These crystals lose solvent to give single crystals of [Pt{4'-(Ph) trpy}(NCS)]SbF6 (1). An X-ray crystal structure determination of 1 shows that the SCN- ion is N-bound and that the cation as a whole is approximately planar. Compound 1 is porous with empty channels that corkscrew through the crystal: this crystal structure is stabilised by extended pi-pi interactions between the planar cations. When a single crystal of 1 is exposed to vapours of acetonitrile the vapours are sorbed without loss of single crystallinity, as confirmed by crystal structure determinations of 1 and 1 center dot CH3CN using the same single crystal. Similarly, single crystals of 1 sorb vapours of methanol without loss of single crystallinity, as confirmed by a crystal structure determination of 1 center dot CH3OH. We also report the crystal structure of 1 center dot(CH3)(2)CO; however, in this case the single crystal was grown directly from acetone. Compound 1 and its solvates are all yellow. Nevertheless, there are differences between the emission spectra recorded for 1 and its solvates in the solid state. Thus, whereas 1 exhibits very weak multiple emission from (MLCT)-M-3 (MLCT = metal-to-ligand charge transfer) and excimeric (3)pi-pi* excited states, 1 center dot CH3CN and 1 center dot(CH3)(2)CO both exhibit more intense 3MLCTemission; and the emission by 1 center dot CH3OH is complicated by the presence of metallophilic interactions in the crystal. We discuss the role of the solvent in causing these differences.
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