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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Platinum
X ray crystallography
Polymers
Single crystals
Phosphorescence
Organometallics
Polycondensation
Thermodynamic stability
Derivatives
Optical spectroscopy
Temperature

ASJC Scopus subject areas

  • Chemistry(all)

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

In: Journal of the Chemical Society, Dalton Transactions, No. 7, 2002, p. 1358-1368.

Research output: Contribution to journalArticle

Khan, Muhammad S. ; Al-Mandhary, Muna R A ; Al-Suti, Mohammed K. ; Hisahm, Abdul Khader ; Raithby, Paul R. ; Ahrens, Birte ; Mahon, Mary F. ; Male, Louise ; Marseglia, Elisabeth A. ; Tedesco, Emilio ; Friend, Richard H. ; Köhler, Anna ; Feederd, Neil ; Teat, Simon J. / 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. In: Journal of the Chemical Society, Dalton Transactions. 2002 ; No. 7. pp. 1358-1368.
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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.",
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AU - Khan, Muhammad S.

AU - Al-Mandhary, Muna R A

AU - Al-Suti, Mohammed K.

AU - Hisahm, Abdul Khader

AU - Raithby, Paul R.

AU - Ahrens, Birte

AU - Mahon, Mary F.

AU - Male, Louise

AU - Marseglia, Elisabeth A.

AU - Tedesco, Emilio

AU - Friend, Richard H.

AU - Köhler, Anna

AU - Feederd, Neil

AU - Teat, Simon J.

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N2 - 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.

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