Synthesis, characterization and photoluminescence of dimeric and polymeric metallaynes of group 10-12 metals containing conjugation-breaking diphenylmethane unit

Wai Yeung WONG; Suk Yue Poon

doi:10.1007/s10904-007-9180-x

Synthesis, characterization and photoluminescence of dimeric and polymeric metallaynes of group 10-12 metals containing conjugation-breaking diphenylmethane unit

Wai Yeung WONG^*, Suk Yue Poon

^*Corresponding author for this work

Department of Chemistry

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

6 Citations (Scopus)

Abstract

A novel approach based on conjugation interruption was developed for a luminescent and thermally stable platinum(II) polyyne polymer trans-[-Pt(PBu ₃) ₂C≡C(C ₆H ₄)CH ₂(C ₆H ₄)C≡C-] _n (1) containing the diphenylmethane chromophoric spacer. Particular attention was focused on the photophysical properties of this group 10 polymetallayne and comparison was made to its binuclear model complex trans-[Pt(Ph)(PEt ₃) ₂C≡C(C ₆H ₄)CH ₂(C ₆H ₄)C≡CPt(Ph)(PEt ₃) ₂] (2) and their closest group 11 gold(I) and group 12 mercury(II) neighbors, [MC≡C(C ₆H ₄)CH ₂(C ₆H ₄)C≡CM] (M = Au(PPh ₃) (3), HgMe (4)). The regiochemical structures of these angular-shaped compounds were studied by various spectroscopic analyses. Upon photoexcitation, each of them emits an intense purple-blue fluorescence emission in the near UV region in dilute fluid solutions at room temperature. Harvesting of organic triplet emissions harnessed through the strong heavy-atom effects of group 10-12 transition metals was examined. These metal-containing phenyleneethynylenes spaced by the conjugation-breaking CH ₂ unit were found to have high optical gaps and high-energy triplet states. The influence of metal and sp ³-hybridized methylene conjugation-interrupters on the intersystem crossing rate and the spatial extent of the lowest singlet and triplet excitons was fully elucidated. Our investigations indicate that high-energy triplet states in these materials intrinsically give rise to very efficient phosphorescence with fast radiative decays.

Original language	English
Pages (from-to)	155-162
Number of pages	8
Journal	Journal of Inorganic and Organometallic Polymers and Materials
Volume	18
Issue number	1
DOIs	https://doi.org/10.1007/s10904-007-9180-x
Publication status	Published - Mar 2008

Scopus Subject Areas

Polymers and Plastics
Materials Chemistry

User-Defined Keywords

Alkyne
Diphenylmethane
Metallopolyyne
Phosphorescence
Transition metal

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10.1007/s10904-007-9180-x

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@article{3f7083096fe24aaba2c634d5da0a7035,

title = "Synthesis, characterization and photoluminescence of dimeric and polymeric metallaynes of group 10-12 metals containing conjugation-breaking diphenylmethane unit",

abstract = "A novel approach based on conjugation interruption was developed for a luminescent and thermally stable platinum(II) polyyne polymer trans-[-Pt(PBu 3) 2C≡C(C 6H 4)CH 2(C 6H 4)C≡C-] n (1) containing the diphenylmethane chromophoric spacer. Particular attention was focused on the photophysical properties of this group 10 polymetallayne and comparison was made to its binuclear model complex trans-[Pt(Ph)(PEt 3) 2C≡C(C 6H 4)CH 2(C 6H 4)C≡CPt(Ph)(PEt 3) 2] (2) and their closest group 11 gold(I) and group 12 mercury(II) neighbors, [MC≡C(C 6H 4)CH 2(C 6H 4)C≡CM] (M = Au(PPh 3) (3), HgMe (4)). The regiochemical structures of these angular-shaped compounds were studied by various spectroscopic analyses. Upon photoexcitation, each of them emits an intense purple-blue fluorescence emission in the near UV region in dilute fluid solutions at room temperature. Harvesting of organic triplet emissions harnessed through the strong heavy-atom effects of group 10-12 transition metals was examined. These metal-containing phenyleneethynylenes spaced by the conjugation-breaking CH 2 unit were found to have high optical gaps and high-energy triplet states. The influence of metal and sp 3-hybridized methylene conjugation-interrupters on the intersystem crossing rate and the spatial extent of the lowest singlet and triplet excitons was fully elucidated. Our investigations indicate that high-energy triplet states in these materials intrinsically give rise to very efficient phosphorescence with fast radiative decays.",

keywords = "Alkyne, Diphenylmethane, Metallopolyyne, Phosphorescence, Transition metal",

author = "WONG, {Wai Yeung} and Poon, {Suk Yue}",

note = "Funding Information: Acknowledgments Financial support from the Hong Kong Research Grants Council (HKBU 2021/06P) and Hong Kong Baptist University (FRG/06-07/II-63) is gratefully acknowledged.",

year = "2008",

month = mar,

doi = "10.1007/s10904-007-9180-x",

language = "English",

volume = "18",

pages = "155--162",

journal = "Journal of Inorganic and Organometallic Polymers and Materials",

issn = "1574-1443",

publisher = "Springer",

number = "1",

}

Synthesis, characterization and photoluminescence of dimeric and polymeric metallaynes of group 10-12 metals containing conjugation-breaking diphenylmethane unit. / WONG, Wai Yeung; Poon, Suk Yue.
In: Journal of Inorganic and Organometallic Polymers and Materials, Vol. 18, No. 1, 03.2008, p. 155-162.

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

TY - JOUR

T1 - Synthesis, characterization and photoluminescence of dimeric and polymeric metallaynes of group 10-12 metals containing conjugation-breaking diphenylmethane unit

AU - WONG, Wai Yeung

AU - Poon, Suk Yue

N1 - Funding Information: Acknowledgments Financial support from the Hong Kong Research Grants Council (HKBU 2021/06P) and Hong Kong Baptist University (FRG/06-07/II-63) is gratefully acknowledged.

PY - 2008/3

Y1 - 2008/3

N2 - A novel approach based on conjugation interruption was developed for a luminescent and thermally stable platinum(II) polyyne polymer trans-[-Pt(PBu 3) 2C≡C(C 6H 4)CH 2(C 6H 4)C≡C-] n (1) containing the diphenylmethane chromophoric spacer. Particular attention was focused on the photophysical properties of this group 10 polymetallayne and comparison was made to its binuclear model complex trans-[Pt(Ph)(PEt 3) 2C≡C(C 6H 4)CH 2(C 6H 4)C≡CPt(Ph)(PEt 3) 2] (2) and their closest group 11 gold(I) and group 12 mercury(II) neighbors, [MC≡C(C 6H 4)CH 2(C 6H 4)C≡CM] (M = Au(PPh 3) (3), HgMe (4)). The regiochemical structures of these angular-shaped compounds were studied by various spectroscopic analyses. Upon photoexcitation, each of them emits an intense purple-blue fluorescence emission in the near UV region in dilute fluid solutions at room temperature. Harvesting of organic triplet emissions harnessed through the strong heavy-atom effects of group 10-12 transition metals was examined. These metal-containing phenyleneethynylenes spaced by the conjugation-breaking CH 2 unit were found to have high optical gaps and high-energy triplet states. The influence of metal and sp 3-hybridized methylene conjugation-interrupters on the intersystem crossing rate and the spatial extent of the lowest singlet and triplet excitons was fully elucidated. Our investigations indicate that high-energy triplet states in these materials intrinsically give rise to very efficient phosphorescence with fast radiative decays.

AB - A novel approach based on conjugation interruption was developed for a luminescent and thermally stable platinum(II) polyyne polymer trans-[-Pt(PBu 3) 2C≡C(C 6H 4)CH 2(C 6H 4)C≡C-] n (1) containing the diphenylmethane chromophoric spacer. Particular attention was focused on the photophysical properties of this group 10 polymetallayne and comparison was made to its binuclear model complex trans-[Pt(Ph)(PEt 3) 2C≡C(C 6H 4)CH 2(C 6H 4)C≡CPt(Ph)(PEt 3) 2] (2) and their closest group 11 gold(I) and group 12 mercury(II) neighbors, [MC≡C(C 6H 4)CH 2(C 6H 4)C≡CM] (M = Au(PPh 3) (3), HgMe (4)). The regiochemical structures of these angular-shaped compounds were studied by various spectroscopic analyses. Upon photoexcitation, each of them emits an intense purple-blue fluorescence emission in the near UV region in dilute fluid solutions at room temperature. Harvesting of organic triplet emissions harnessed through the strong heavy-atom effects of group 10-12 transition metals was examined. These metal-containing phenyleneethynylenes spaced by the conjugation-breaking CH 2 unit were found to have high optical gaps and high-energy triplet states. The influence of metal and sp 3-hybridized methylene conjugation-interrupters on the intersystem crossing rate and the spatial extent of the lowest singlet and triplet excitons was fully elucidated. Our investigations indicate that high-energy triplet states in these materials intrinsically give rise to very efficient phosphorescence with fast radiative decays.

KW - Alkyne

KW - Diphenylmethane

KW - Metallopolyyne

KW - Phosphorescence

KW - Transition metal

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U2 - 10.1007/s10904-007-9180-x

DO - 10.1007/s10904-007-9180-x

M3 - Journal article

AN - SCOPUS:38449089324

SN - 1574-1443

VL - 18

SP - 155

EP - 162

JO - Journal of Inorganic and Organometallic Polymers and Materials

JF - Journal of Inorganic and Organometallic Polymers and Materials

IS - 1

ER -

Synthesis, characterization and photoluminescence of dimeric and polymeric metallaynes of group 10-12 metals containing conjugation-breaking diphenylmethane unit

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