Structural characterisation of a series of acetylide-functionalised oligopyridines and the synthesis, characterisation and optical spectroscopy of platinum di-ynes and poly-ynes containing oligopyridyl linker groups in the backbone

Muhammad S. Khan, Muna R A Al-Mandhary, Mohammed K. Al-Suti, Abdul Khader Hisahm, Paul R. Raithby, Birte Ahrens, Mary F. Mahon, Louise Male, Elisabeth A. Marseglia, Emilio Tedesco, Richard H. Friend, Anna Köhler, Neil Feederd, Simon J. Teat

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Abstract

A series of trimethylsilyl-protected bis(ethynyl)oligopyridine derivatives Me3SiC≡C-R-C≡C-SiMe3 (R = 2,2′-bipyridine-5,5′-diyl (1a), 2,2′-bipyridine-6,6′-diyl (2a), 2,2′:6′,2″-terpyridine-6,6″-diyl (3a), 4′-phenyl-2,2′:6′,2″-terpyridine-6,6″-diyl (4a)) has been synthesised and 2a-4a have been characterised by single crystal X-ray crystallography. The corresponding terminal di-ynes H-C≡C-R-C≡CH (1b-4b) and their dinuclear platinum(II) complexes trans-[(Et3P)2(Ph)Pt-C≡C-R-C≡C-Pt(Ph) (Et3P)2] (1M-4M) have been characterised spectroscopically and by single-crystal X-ray crystallography for 2M. Novel platinum(II) poly-yne polymers trans-[Pt(PBun 3)2-C≡C-R-C≡C-] n (1P-4P) containing the oligopyridyl linker groups in the backbone have been synthesised by the CuI-catalysed dehydrohalogenation polycondensation reaction of 1b-4b and trans-[(Bu3P)2PtCl2] in Pri 2NH-CH2Cl2. The polymeric materials exhibit decreasing thermal stability with increasing number of pyridine units in the linker group. In the absorption and phosphorescence spectra, the platinum(II) poly-yne and di-yne complexes 1P, 1M show red shifts whereas the complexes 2P-3P, 2M-3M show blue shifts of the S1 and T1 states. At room temperature, the phosphoresence spectra indicate some excimer formation whereas at 10 K, only intra-chain emission occurs. The results of the photophysical studies are compared with those obtained for other platinum(II)-containing poly-ynes and related organometallic polymers.

Original languageEnglish
Pages (from-to)1358-1368
Number of pages11
JournalJournal of the Chemical Society, Dalton Transactions
Issue number7
Publication statusPublished - 2002

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ASJC Scopus subject areas

  • Chemistry(all)

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