Effect of acetylenic chain length on the tuning of functional properties in fluorene-bridged polymetallaynes and their molecular model compounds

Li Liu; Wai Yeung Wong; Suk Yue Poon; Jian Xin Shi; Kok Wai Cheah; Zhenyang Lin

doi:10.1021/cm052655a

Effect of acetylenic chain length on the tuning of functional properties in fluorene-bridged polymetallaynes and their molecular model compounds

Li Liu, Wai Yeung Wong^*, Suk Yue Poon, Jian Xin Shi, Kok Wai Cheah, Zhenyang Lin

^*Corresponding author for this work

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

56 Citations (Scopus)

Abstract

We describe for the first time thermally stable and high-molecular-weight group 10 platinum(II) and group 12 mercury(II) polyyne polymers consisting of 2,7-bis(buta-1,3-diynyl)-9,9-dihexylfluorene linking units trans-[- Pt(PBu ₃)₂(C≡C)₂R(C≡C)₂-] _n and [-Hg(C≡C)₂R(C≡C)₂-] _n (R = 9,9-dihexylfluorene-2,7-diyl). The optical absorption and photoluminescence spectra of these carbon-rich metallopolymers were examined and compared with their dinuclear model complexes trans-[Pt(Ph)(PEt ₃)₂(C≡C)₂R-(C≡C) ₂Pt(Ph)(PEt₃)₂] and [MeHg(C≡C) ₂R(C≡C)₂HgMe] as well as the group 11 gold(I) congener [(PPh₃)-Au(C≡C)₂R(C≡C) ₂Au(PPh₃)]. The regiochemical structures of the polymers were studied by NMR spectroscopy and ascertained by single-crystal X-ray structural analysis for the model platinum(II) compound. The heavy-atom effects of group 10-12 transition metals in triplet light energy harvesting and the influence of the C≡C chain length on the spatial extent of singlet and triplet excitons in metalated systems of the form [-M(C≡C) _mR(C≡C)_mM-]_n (M = Pt, Au, or Hg chromophore; m = 1, 2) are systematically characterized. The dependence of the optical energy gap as a function of the acetylenic chain length for the platinum system was probed by both optical methods and molecular orbital calculations, and a linear correlation was derived between the highest occupied molecular orbital-lowest unoccupied molecular orbital gap and 1/m². An extension of the C≡C unit gives rise to a state of lower triplet energy and is accompanied by a decrease in the triplet quantum yield and lifetime, in accordance with the energy gap law for the triplet states in metal polyynes.

Original language	English
Pages (from-to)	1369-1378
Number of pages	10
Journal	Chemistry of Materials
Volume	18
Issue number	5
DOIs	https://doi.org/10.1021/cm052655a
Publication status	Published - 7 Mar 2006

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10.1021/cm052655a

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@article{e02e247901434d2385798979786f5a86,

title = "Effect of acetylenic chain length on the tuning of functional properties in fluorene-bridged polymetallaynes and their molecular model compounds",

abstract = "We describe for the first time thermally stable and high-molecular-weight group 10 platinum(II) and group 12 mercury(II) polyyne polymers consisting of 2,7-bis(buta-1,3-diynyl)-9,9-dihexylfluorene linking units trans-[- Pt(PBu 3)2(C≡C)2R(C≡C)2-] n and [-Hg(C≡C)2R(C≡C)2-] n (R = 9,9-dihexylfluorene-2,7-diyl). The optical absorption and photoluminescence spectra of these carbon-rich metallopolymers were examined and compared with their dinuclear model complexes trans-[Pt(Ph)(PEt 3)2(C≡C)2R-(C≡C) 2Pt(Ph)(PEt3)2] and [MeHg(C≡C) 2R(C≡C)2HgMe] as well as the group 11 gold(I) congener [(PPh3)-Au(C≡C)2R(C≡C) 2Au(PPh3)]. The regiochemical structures of the polymers were studied by NMR spectroscopy and ascertained by single-crystal X-ray structural analysis for the model platinum(II) compound. The heavy-atom effects of group 10-12 transition metals in triplet light energy harvesting and the influence of the C≡C chain length on the spatial extent of singlet and triplet excitons in metalated systems of the form [-M(C≡C) mR(C≡C)mM-]n (M = Pt, Au, or Hg chromophore; m = 1, 2) are systematically characterized. The dependence of the optical energy gap as a function of the acetylenic chain length for the platinum system was probed by both optical methods and molecular orbital calculations, and a linear correlation was derived between the highest occupied molecular orbital-lowest unoccupied molecular orbital gap and 1/m2. An extension of the C≡C unit gives rise to a state of lower triplet energy and is accompanied by a decrease in the triplet quantum yield and lifetime, in accordance with the energy gap law for the triplet states in metal polyynes.",

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

note = "Financial support from the Hong Kong Research Grants Council (HKBU2022/03P) and Hong Kong Baptist University (FRG/03-04/II-69) is gratefully acknowledged.",

year = "2006",

month = mar,

day = "7",

doi = "10.1021/cm052655a",

language = "English",

volume = "18",

pages = "1369--1378",

journal = "Chemistry of Materials",

issn = "0897-4756",

publisher = "American Chemical Society",

number = "5",

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TY - JOUR

T1 - Effect of acetylenic chain length on the tuning of functional properties in fluorene-bridged polymetallaynes and their molecular model compounds

AU - Liu, Li

AU - Wong, Wai Yeung

AU - Poon, Suk Yue

AU - Shi, Jian Xin

AU - Cheah, Kok Wai

AU - Lin, Zhenyang

N1 - Financial support from the Hong Kong Research Grants Council (HKBU2022/03P) and Hong Kong Baptist University (FRG/03-04/II-69) is gratefully acknowledged.

PY - 2006/3/7

Y1 - 2006/3/7

N2 - We describe for the first time thermally stable and high-molecular-weight group 10 platinum(II) and group 12 mercury(II) polyyne polymers consisting of 2,7-bis(buta-1,3-diynyl)-9,9-dihexylfluorene linking units trans-[- Pt(PBu 3)2(C≡C)2R(C≡C)2-] n and [-Hg(C≡C)2R(C≡C)2-] n (R = 9,9-dihexylfluorene-2,7-diyl). The optical absorption and photoluminescence spectra of these carbon-rich metallopolymers were examined and compared with their dinuclear model complexes trans-[Pt(Ph)(PEt 3)2(C≡C)2R-(C≡C) 2Pt(Ph)(PEt3)2] and [MeHg(C≡C) 2R(C≡C)2HgMe] as well as the group 11 gold(I) congener [(PPh3)-Au(C≡C)2R(C≡C) 2Au(PPh3)]. The regiochemical structures of the polymers were studied by NMR spectroscopy and ascertained by single-crystal X-ray structural analysis for the model platinum(II) compound. The heavy-atom effects of group 10-12 transition metals in triplet light energy harvesting and the influence of the C≡C chain length on the spatial extent of singlet and triplet excitons in metalated systems of the form [-M(C≡C) mR(C≡C)mM-]n (M = Pt, Au, or Hg chromophore; m = 1, 2) are systematically characterized. The dependence of the optical energy gap as a function of the acetylenic chain length for the platinum system was probed by both optical methods and molecular orbital calculations, and a linear correlation was derived between the highest occupied molecular orbital-lowest unoccupied molecular orbital gap and 1/m2. An extension of the C≡C unit gives rise to a state of lower triplet energy and is accompanied by a decrease in the triplet quantum yield and lifetime, in accordance with the energy gap law for the triplet states in metal polyynes.

AB - We describe for the first time thermally stable and high-molecular-weight group 10 platinum(II) and group 12 mercury(II) polyyne polymers consisting of 2,7-bis(buta-1,3-diynyl)-9,9-dihexylfluorene linking units trans-[- Pt(PBu 3)2(C≡C)2R(C≡C)2-] n and [-Hg(C≡C)2R(C≡C)2-] n (R = 9,9-dihexylfluorene-2,7-diyl). The optical absorption and photoluminescence spectra of these carbon-rich metallopolymers were examined and compared with their dinuclear model complexes trans-[Pt(Ph)(PEt 3)2(C≡C)2R-(C≡C) 2Pt(Ph)(PEt3)2] and [MeHg(C≡C) 2R(C≡C)2HgMe] as well as the group 11 gold(I) congener [(PPh3)-Au(C≡C)2R(C≡C) 2Au(PPh3)]. The regiochemical structures of the polymers were studied by NMR spectroscopy and ascertained by single-crystal X-ray structural analysis for the model platinum(II) compound. The heavy-atom effects of group 10-12 transition metals in triplet light energy harvesting and the influence of the C≡C chain length on the spatial extent of singlet and triplet excitons in metalated systems of the form [-M(C≡C) mR(C≡C)mM-]n (M = Pt, Au, or Hg chromophore; m = 1, 2) are systematically characterized. The dependence of the optical energy gap as a function of the acetylenic chain length for the platinum system was probed by both optical methods and molecular orbital calculations, and a linear correlation was derived between the highest occupied molecular orbital-lowest unoccupied molecular orbital gap and 1/m2. An extension of the C≡C unit gives rise to a state of lower triplet energy and is accompanied by a decrease in the triplet quantum yield and lifetime, in accordance with the energy gap law for the triplet states in metal polyynes.

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DO - 10.1021/cm052655a

M3 - Journal article

AN - SCOPUS:33644934183

SN - 0897-4756

VL - 18

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EP - 1378

JO - Chemistry of Materials

JF - Chemistry of Materials

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ER -

Effect of acetylenic chain length on the tuning of functional properties in fluorene-bridged polymetallaynes and their molecular model compounds

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