Evolution of lowest singlet and triplet excited states with number of thienyl rings in platinum poly-ynes

N. Chawdhury, A. Köhler, R. H. Friend, W. Y. Wong, J. Lewis, M. Younus, P. R. Raithby, T. C. Corcoran, M. R A Al-Mandhary, M. S. Khan

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Abstract

Soluble, rigid-rod organometallic polymers trans-[-Pt(PBun 3) 2-C≡C-R-C≡C-]∝ (R=bithienyl 2, terthienyl 3) have been synthesized in good yields by the CuI-catalyzed dehydrohalogenation reaction of trans-[Pt(PBUn 3)2Cl2] with one equivalent of the diterminal alkynyl oligothiophenes H-C≡C-R-C≡C-H in CH2Cl2/iPr2NH at room temperature. We report the thermal properties, and the optical absorption, photoluminescence, and photocurrent action spectra of 1 (trans-[-Pt(PBUn 3) 2-C≡C-R-C≡C-]∝, R=thienyl), 2 and 3 as a function of the number of thiophene rings within the bridging ligand. With increasing thiophene content, the optical gap is reduced and the vibronic structure of the singlet emission changes toward that typical for oligothiophenes. We also find the intersystem crossing from the singlet excited state to the triplet excited state to become reduced, while the singlet-triplet energy gap remains unaltered. The latter implies that, in these systems, the T1 triplet excited state is extended over several thiophene rings. The photoconducting properties do not depend on the size of the thiophene fragment. We discuss and compare our results with studies on oligothiophenes and related organometallic polymers.

Original languageEnglish
Pages (from-to)4963-4970
Number of pages8
JournalJournal of Chemical Physics
Volume110
Issue number10
Publication statusPublished - Mar 8 1999

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Thiophenes
thiophenes
Platinum
Excited states
platinum
organometallic polymers
rings
Organometallics
excitation
Polymers
Photocurrents
Light absorption
photocurrents
Photoluminescence
Energy gap
optical absorption
rods
Thermodynamic properties
thermodynamic properties
fragments

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics

Cite this

Chawdhury, N., Köhler, A., Friend, R. H., Wong, W. Y., Lewis, J., Younus, M., ... Khan, M. S. (1999). Evolution of lowest singlet and triplet excited states with number of thienyl rings in platinum poly-ynes. Journal of Chemical Physics, 110(10), 4963-4970.

Evolution of lowest singlet and triplet excited states with number of thienyl rings in platinum poly-ynes. / Chawdhury, N.; Köhler, A.; Friend, R. H.; Wong, W. Y.; Lewis, J.; Younus, M.; Raithby, P. R.; Corcoran, T. C.; Al-Mandhary, M. R A; Khan, M. S.

In: Journal of Chemical Physics, Vol. 110, No. 10, 08.03.1999, p. 4963-4970.

Research output: Contribution to journalArticle

Chawdhury, N, Köhler, A, Friend, RH, Wong, WY, Lewis, J, Younus, M, Raithby, PR, Corcoran, TC, Al-Mandhary, MRA & Khan, MS 1999, 'Evolution of lowest singlet and triplet excited states with number of thienyl rings in platinum poly-ynes', Journal of Chemical Physics, vol. 110, no. 10, pp. 4963-4970.
Chawdhury N, Köhler A, Friend RH, Wong WY, Lewis J, Younus M et al. Evolution of lowest singlet and triplet excited states with number of thienyl rings in platinum poly-ynes. Journal of Chemical Physics. 1999 Mar 8;110(10):4963-4970.
Chawdhury, N. ; Köhler, A. ; Friend, R. H. ; Wong, W. Y. ; Lewis, J. ; Younus, M. ; Raithby, P. R. ; Corcoran, T. C. ; Al-Mandhary, M. R A ; Khan, M. S. / Evolution of lowest singlet and triplet excited states with number of thienyl rings in platinum poly-ynes. In: Journal of Chemical Physics. 1999 ; Vol. 110, No. 10. pp. 4963-4970.
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AU - Lewis, J.

AU - Younus, M.

AU - Raithby, P. R.

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AU - Khan, M. S.

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N2 - Soluble, rigid-rod organometallic polymers trans-[-Pt(PBun 3) 2-C≡C-R-C≡C-]∝ (R=bithienyl 2, terthienyl 3) have been synthesized in good yields by the CuI-catalyzed dehydrohalogenation reaction of trans-[Pt(PBUn 3)2Cl2] with one equivalent of the diterminal alkynyl oligothiophenes H-C≡C-R-C≡C-H in CH2Cl2/iPr2NH at room temperature. We report the thermal properties, and the optical absorption, photoluminescence, and photocurrent action spectra of 1 (trans-[-Pt(PBUn 3) 2-C≡C-R-C≡C-]∝, R=thienyl), 2 and 3 as a function of the number of thiophene rings within the bridging ligand. With increasing thiophene content, the optical gap is reduced and the vibronic structure of the singlet emission changes toward that typical for oligothiophenes. We also find the intersystem crossing from the singlet excited state to the triplet excited state to become reduced, while the singlet-triplet energy gap remains unaltered. The latter implies that, in these systems, the T1 triplet excited state is extended over several thiophene rings. The photoconducting properties do not depend on the size of the thiophene fragment. We discuss and compare our results with studies on oligothiophenes and related organometallic polymers.

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