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Synthesis, Characterization and Optoelectronic Properties of Dimeric and Polymeric Metallaynes Derived from 3,6-Bis(buta-1,3-diynyl)-9-butylcarbazole

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A thermally stable platinum(II) polyyne polymer incorporating carbazole-based linking units, trans-[–Pt(PBu3)2C≡CC≡CRC≡CC≡C–] n (R = 9-butylcarbazole-3,6-diyl), was prepared by polycondensation polymerization of trans-[PtCl2(PBu3)2] with H–C≡CC≡CRC≡CC≡C–H. We report the optical absorption and photoluminescence spectra of this carbon-rich metallopolymer and compare its photophysics with its molecular dinuclear model complex trans-[Pt(Ph)(PEt3)2C≡CC≡CRC≡CC≡CPt(Ph)(PEt3)2] as well as the group 11 gold(I) congener, [(PPh3)AuC≡CC≡CRC≡CC≡CAu(PPh3)]. Characterization of the polymer and metal complexes was accomplished by FT-IR and NMR spectroscopies and FAB mass spectrometry. Our investigations showed that harvesting of the organic triplet emissions can be achieved by the heavy-atom effect of Pt and Au centers, which enables a very high efficiency of intersystem crossing from the S1 singlet excited state to the T1 triplet excited state. The influence of the metal and the C≡C chain length on the intersystem crossing rate and the spatial extent of singlet and triplet excitons is characterized. The present work indicates that high-energy triplet states intrinsically give more efficient phosphorescence in metal-containing diethynylcarbazole systems than in the corresponding bis(butadiynyl) congeners and can thus enhance the radiative decay pathway.

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ACKNOWLEDGMENTS

Financial support from the Hong Kong Research Grants Council (HKBU 2022/03P) and Hong Kong Baptist University (FRG/03-04/II-69) is gratefully acknowledged.

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Authors and Affiliations

  1. Faculty of Chemistry and Material Science, Hubei University, Wuhan, 430062, P.R. China

    Li Liu

  2. Department of Chemistry and Centre for Advanced Luminescence Materials, Hong Kong Baptist University, Waterloo Road, Kowloon Tong, Hong Kong, P.R. China

    Li Liu, Wai-Yeung Wong & Suk-Yue Poon

  3. Department of Physics and Centre for Advanced Luminescence Materials, Hong Kong Baptist University, Waterloo Road, Kowloon Tong, Hong Kong, P.R. China

    Kok-Wai Cheah

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  1. Li Liu
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Correspondence to Wai-Yeung Wong.

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Dedicated to Professor Richard J. Puddephatt in recognition of his outstanding contribution to inorganic and organometallic chemistry.

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Liu, L., Wong, WY., Poon, SY. et al. Synthesis, Characterization and Optoelectronic Properties of Dimeric and Polymeric Metallaynes Derived from 3,6-Bis(buta-1,3-diynyl)-9-butylcarbazole. J Inorg Organomet Polym 15, 555–567 (2005). https://doi.org/10.1007/s10904-006-9009-z

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