Harvesting of organic triplet emissions in metal diynes and polyynes of group 10-12 transition elements containing the conjugation-interrupting diphenylfluorene unit

Wai Yeung Wong; Li Liu; Suk Yue Poon; Ka Ho Choi; Kok Wai Cheah; Jian Xin Shi

doi:10.1021/ma049773o

Harvesting of organic triplet emissions in metal diynes and polyynes of group 10-12 transition elements containing the conjugation-interrupting diphenylfluorene unit

Wai Yeung Wong^*, Li Liu, Suk Yue Poon, Ka Ho Choi, Kok Wai Cheah, Jian Xin Shi

^*Corresponding author for this work

Research output: Contribution to journal › Journal article › peer-review

82 Citations (Scopus)

Abstract

Soluble and thermally stable group 10 platinum(II) and group 12 mercury(II) polyyne polymers containing the diphenylfluorene moiety trans-[-Pt(PBu ₃)₂C≡CRC≡C-]_n and [-HgC≡CRC≡ C-]_n (R = 9,9-diphenylfluorene) were prepared in good yields by polycondensation polymerization of trans[PtCl ₂(PBu₃)₂] or HgCl₂ with 9,9-bis(4-ethynylphenyl)fluorene. We report the optical absorption and photoluminescence spectra of these carbon-rich metal-based polymers and compare the results with their monomeric model complexes trans-[Pt(Ph)(PEt ₃)₂C≡CRC≡CPt(Ph)(PEt₃) ₂] and [MeHgC≡CRC≡CHgMe] as well as the group 11 gold(I) congener [(PPh₃)AuC≡CRC≡CAu(PPh₃)]. The regiochemical structures of the polymers were studied by NMR spectroscopy and by single-crystal X-ray analysis for the model platinum(II) compound. Our investigations indicate that harvesting of the organic triplet emissions can be achieved by the heavy-atom effect of group 10-12 transition metals (i.e., Pt, Au, Hg) 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 fluorene ring on the intersystem crossing rate and the spatial extent of singlet and triplet excitons is characterized. These phosphorescent metal-organic materials show T₁-S₀ gaps of 2.5 eV or above, which correspond to S₁-S₀ gaps of 3.1 eV or higher. The present work indicates that high-energy triplet states (and concurrently high optical gaps) intrinsically lead to more efficient phosphorescence in metal-containing aryleneethynylenes and can facilitate the radiative decay pathway.

Original language	English
Pages (from-to)	4496-4504
Number of pages	9
Journal	Macromolecules
Volume	37
Issue number	12
DOIs	https://doi.org/10.1021/ma049773o
Publication status	Published - 15 Jun 2004

Scopus Subject Areas

Organic Chemistry
Polymers and Plastics
Inorganic Chemistry
Materials Chemistry

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@article{7ed48f486bf0440dadea885200cd6458,

title = "Harvesting of organic triplet emissions in metal diynes and polyynes of group 10-12 transition elements containing the conjugation-interrupting diphenylfluorene unit",

abstract = "Soluble and thermally stable group 10 platinum(II) and group 12 mercury(II) polyyne polymers containing the diphenylfluorene moiety trans-[-Pt(PBu 3)2C≡CRC≡C-]n and [-HgC≡CRC≡ C-]n (R = 9,9-diphenylfluorene) were prepared in good yields by polycondensation polymerization of trans[PtCl 2(PBu3)2] or HgCl2 with 9,9-bis(4-ethynylphenyl)fluorene. We report the optical absorption and photoluminescence spectra of these carbon-rich metal-based polymers and compare the results with their monomeric model complexes trans-[Pt(Ph)(PEt 3)2C≡CRC≡CPt(Ph)(PEt3) 2] and [MeHgC≡CRC≡CHgMe] as well as the group 11 gold(I) congener [(PPh3)AuC≡CRC≡CAu(PPh3)]. The regiochemical structures of the polymers were studied by NMR spectroscopy and by single-crystal X-ray analysis for the model platinum(II) compound. Our investigations indicate that harvesting of the organic triplet emissions can be achieved by the heavy-atom effect of group 10-12 transition metals (i.e., Pt, Au, Hg) 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 fluorene ring on the intersystem crossing rate and the spatial extent of singlet and triplet excitons is characterized. These phosphorescent metal-organic materials show T1-S0 gaps of 2.5 eV or above, which correspond to S1-S0 gaps of 3.1 eV or higher. The present work indicates that high-energy triplet states (and concurrently high optical gaps) intrinsically lead to more efficient phosphorescence in metal-containing aryleneethynylenes and can facilitate the radiative decay pathway.",

author = "Wong, {Wai Yeung} and Li Liu and Poon, {Suk Yue} and Choi, {Ka Ho} and Cheah, {Kok Wai} and Shi, {Jian Xin}",

note = "We are grateful to the Hong Kong Research Grants Council (Grants HKBU 2048/ 01P and 2022/03P) and the Hong Kong Baptist University (FRG/01-02/II-48) for financial support. We also thank Miss Carmen Ng for helpful discussions. ",

year = "2004",

month = jun,

day = "15",

doi = "10.1021/ma049773o",

language = "English",

volume = "37",

pages = "4496--4504",

journal = "Macromolecules",

issn = "0024-9297",

publisher = "American Chemical Society",

number = "12",

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T1 - Harvesting of organic triplet emissions in metal diynes and polyynes of group 10-12 transition elements containing the conjugation-interrupting diphenylfluorene unit

AU - Wong, Wai Yeung

AU - Liu, Li

AU - Poon, Suk Yue

AU - Choi, Ka Ho

AU - Cheah, Kok Wai

AU - Shi, Jian Xin

N1 - We are grateful to the Hong Kong Research Grants Council (Grants HKBU 2048/ 01P and 2022/03P) and the Hong Kong Baptist University (FRG/01-02/II-48) for financial support. We also thank Miss Carmen Ng for helpful discussions.

PY - 2004/6/15

Y1 - 2004/6/15

N2 - Soluble and thermally stable group 10 platinum(II) and group 12 mercury(II) polyyne polymers containing the diphenylfluorene moiety trans-[-Pt(PBu 3)2C≡CRC≡C-]n and [-HgC≡CRC≡ C-]n (R = 9,9-diphenylfluorene) were prepared in good yields by polycondensation polymerization of trans[PtCl 2(PBu3)2] or HgCl2 with 9,9-bis(4-ethynylphenyl)fluorene. We report the optical absorption and photoluminescence spectra of these carbon-rich metal-based polymers and compare the results with their monomeric model complexes trans-[Pt(Ph)(PEt 3)2C≡CRC≡CPt(Ph)(PEt3) 2] and [MeHgC≡CRC≡CHgMe] as well as the group 11 gold(I) congener [(PPh3)AuC≡CRC≡CAu(PPh3)]. The regiochemical structures of the polymers were studied by NMR spectroscopy and by single-crystal X-ray analysis for the model platinum(II) compound. Our investigations indicate that harvesting of the organic triplet emissions can be achieved by the heavy-atom effect of group 10-12 transition metals (i.e., Pt, Au, Hg) 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 fluorene ring on the intersystem crossing rate and the spatial extent of singlet and triplet excitons is characterized. These phosphorescent metal-organic materials show T1-S0 gaps of 2.5 eV or above, which correspond to S1-S0 gaps of 3.1 eV or higher. The present work indicates that high-energy triplet states (and concurrently high optical gaps) intrinsically lead to more efficient phosphorescence in metal-containing aryleneethynylenes and can facilitate the radiative decay pathway.

AB - Soluble and thermally stable group 10 platinum(II) and group 12 mercury(II) polyyne polymers containing the diphenylfluorene moiety trans-[-Pt(PBu 3)2C≡CRC≡C-]n and [-HgC≡CRC≡ C-]n (R = 9,9-diphenylfluorene) were prepared in good yields by polycondensation polymerization of trans[PtCl 2(PBu3)2] or HgCl2 with 9,9-bis(4-ethynylphenyl)fluorene. We report the optical absorption and photoluminescence spectra of these carbon-rich metal-based polymers and compare the results with their monomeric model complexes trans-[Pt(Ph)(PEt 3)2C≡CRC≡CPt(Ph)(PEt3) 2] and [MeHgC≡CRC≡CHgMe] as well as the group 11 gold(I) congener [(PPh3)AuC≡CRC≡CAu(PPh3)]. The regiochemical structures of the polymers were studied by NMR spectroscopy and by single-crystal X-ray analysis for the model platinum(II) compound. Our investigations indicate that harvesting of the organic triplet emissions can be achieved by the heavy-atom effect of group 10-12 transition metals (i.e., Pt, Au, Hg) 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 fluorene ring on the intersystem crossing rate and the spatial extent of singlet and triplet excitons is characterized. These phosphorescent metal-organic materials show T1-S0 gaps of 2.5 eV or above, which correspond to S1-S0 gaps of 3.1 eV or higher. The present work indicates that high-energy triplet states (and concurrently high optical gaps) intrinsically lead to more efficient phosphorescence in metal-containing aryleneethynylenes and can facilitate the radiative decay pathway.

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U2 - 10.1021/ma049773o

DO - 10.1021/ma049773o

M3 - Journal article

AN - SCOPUS:3042565721

SN - 0024-9297

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JO - Macromolecules

JF - Macromolecules

IS - 12

ER -

Harvesting of organic triplet emissions in metal diynes and polyynes of group 10-12 transition elements containing the conjugation-interrupting diphenylfluorene unit

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