Synthesis and characterisation of new acetylide-functionalised aromatic and hetero-aromatic ligands and their dinuclear platinum complexes

Muhammad S. Khan, Mohammed K. Al-Suti, Muna R A Al-Mandhary, Birte Ahrens, Jens K. Bjernemose, Mary F. Mahon, Louise Male, Paul R. Raithby, Richard H. Friend, Anna Köhler, Joanne S. Wilson

Research output: Contribution to journalArticle

45 Citations (Scopus)

Abstract

A new series of rigid rod protected and terminal dialkynes with extended π-conjugation through aromatic and hetero-aromatic linker units in the backbone, 2,5-bis(trimethylsilylethynyl)-1-(2-ethylhexyloxy)-4-methoxybenzene la, 2,5-bis(ethynyl)-1-(2-ethylhexyloxy)-4-methoxybenzene 1b, 5,8-bis(trimethylsilylethynyl)quinoline 2a, 5,8-bis(ethynyl)quinoline 2b, 2,3-diphenyl-5,8-bis(trimethylsilylethynyl)quinoxaline 3a, 2,3-diphenyl-5, 8-bis(ethynyl)quinoxaline 3b, 4,7-bis(trimethysilylethynyl)-2,1,3-benzothiadiazole 4a and 4,7-bis(ethynyl)-2,1,3-benzothiadiazole 4b, has been synthesised. Treatment of the complex trans-[Pt(Ph)(Cl)(Et3P)2] with half an equivalent of the diterminal alkynes 1b-4b in iPr 2NH-CH2Cl2, in the presence of CuI, at room temperature, afforded the platinum(II) di-yne complexes trans-[(Et 3P)2(Ph)Pt-C≡C-R-C≡C-Pt(Ph)(Et 3P)2] [R = 1-(2-ethylhexyloxy)-4-methoxybenzene-2,5-diyl 1c, quninoline-5,8-diyl 2c, 2,3-diphenylquinoxaline-5,8-diyl 3c, 2,1,3-benzothiadiazole-4,7-diyl 4c] in good yields. The new acetylide-functionalised ligands and the platinum(II) σ-acetylide complexes have been characterised by analytical and spectroscopic methods and X-ray single crystal structure determinations for 2c-4c. The absorption spectra of the complexes 2c-4c show substantial donor-acceptor interaction between the platinum(II) centres and the conjugated ligands. The photoluminescence spectra of 1c-3c show characteristic singlet (S1) and triplet (T 1) emissions. Both the singlet and triplet emissions as well as the absorption decrease in energy with increasing electronegativity of the spacer groups along the series 1c-4c.

Original languageEnglish
Pages (from-to)65-73
Number of pages9
JournalDalton Transactions
Issue number1
DOIs
Publication statusPublished - Jan 7 2003

Fingerprint

Platinum
Quinoxalines
Ligands
Electronegativity
Alkynes
Absorption spectra
Photoluminescence
Crystal structure
Single crystals
X rays
benzo-1,2,3-thiadiazole
anisole
Temperature
quinoline
diphenyl

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

Synthesis and characterisation of new acetylide-functionalised aromatic and hetero-aromatic ligands and their dinuclear platinum complexes. / Khan, Muhammad S.; Al-Suti, Mohammed K.; Al-Mandhary, Muna R A; Ahrens, Birte; Bjernemose, Jens K.; Mahon, Mary F.; Male, Louise; Raithby, Paul R.; Friend, Richard H.; Köhler, Anna; Wilson, Joanne S.

In: Dalton Transactions, No. 1, 07.01.2003, p. 65-73.

Research output: Contribution to journalArticle

Khan, Muhammad S. ; Al-Suti, Mohammed K. ; Al-Mandhary, Muna R A ; Ahrens, Birte ; Bjernemose, Jens K. ; Mahon, Mary F. ; Male, Louise ; Raithby, Paul R. ; Friend, Richard H. ; Köhler, Anna ; Wilson, Joanne S. / Synthesis and characterisation of new acetylide-functionalised aromatic and hetero-aromatic ligands and their dinuclear platinum complexes. In: Dalton Transactions. 2003 ; No. 1. pp. 65-73.
@article{3c97ade3f64d4ee5ac5a11904a149e14,
title = "Synthesis and characterisation of new acetylide-functionalised aromatic and hetero-aromatic ligands and their dinuclear platinum complexes",
abstract = "A new series of rigid rod protected and terminal dialkynes with extended π-conjugation through aromatic and hetero-aromatic linker units in the backbone, 2,5-bis(trimethylsilylethynyl)-1-(2-ethylhexyloxy)-4-methoxybenzene la, 2,5-bis(ethynyl)-1-(2-ethylhexyloxy)-4-methoxybenzene 1b, 5,8-bis(trimethylsilylethynyl)quinoline 2a, 5,8-bis(ethynyl)quinoline 2b, 2,3-diphenyl-5,8-bis(trimethylsilylethynyl)quinoxaline 3a, 2,3-diphenyl-5, 8-bis(ethynyl)quinoxaline 3b, 4,7-bis(trimethysilylethynyl)-2,1,3-benzothiadiazole 4a and 4,7-bis(ethynyl)-2,1,3-benzothiadiazole 4b, has been synthesised. Treatment of the complex trans-[Pt(Ph)(Cl)(Et3P)2] with half an equivalent of the diterminal alkynes 1b-4b in iPr 2NH-CH2Cl2, in the presence of CuI, at room temperature, afforded the platinum(II) di-yne complexes trans-[(Et 3P)2(Ph)Pt-C≡C-R-C≡C-Pt(Ph)(Et 3P)2] [R = 1-(2-ethylhexyloxy)-4-methoxybenzene-2,5-diyl 1c, quninoline-5,8-diyl 2c, 2,3-diphenylquinoxaline-5,8-diyl 3c, 2,1,3-benzothiadiazole-4,7-diyl 4c] in good yields. The new acetylide-functionalised ligands and the platinum(II) σ-acetylide complexes have been characterised by analytical and spectroscopic methods and X-ray single crystal structure determinations for 2c-4c. The absorption spectra of the complexes 2c-4c show substantial donor-acceptor interaction between the platinum(II) centres and the conjugated ligands. The photoluminescence spectra of 1c-3c show characteristic singlet (S1) and triplet (T 1) emissions. Both the singlet and triplet emissions as well as the absorption decrease in energy with increasing electronegativity of the spacer groups along the series 1c-4c.",
author = "Khan, {Muhammad S.} and Al-Suti, {Mohammed K.} and Al-Mandhary, {Muna R A} and Birte Ahrens and Bjernemose, {Jens K.} and Mahon, {Mary F.} and Louise Male and Raithby, {Paul R.} and Friend, {Richard H.} and Anna K{\"o}hler and Wilson, {Joanne S.}",
year = "2003",
month = "1",
day = "7",
doi = "10.1039/b208494e",
language = "English",
pages = "65--73",
journal = "Dalton Transactions",
issn = "1477-9226",
publisher = "Royal Society of Chemistry",
number = "1",

}

TY - JOUR

T1 - Synthesis and characterisation of new acetylide-functionalised aromatic and hetero-aromatic ligands and their dinuclear platinum complexes

AU - Khan, Muhammad S.

AU - Al-Suti, Mohammed K.

AU - Al-Mandhary, Muna R A

AU - Ahrens, Birte

AU - Bjernemose, Jens K.

AU - Mahon, Mary F.

AU - Male, Louise

AU - Raithby, Paul R.

AU - Friend, Richard H.

AU - Köhler, Anna

AU - Wilson, Joanne S.

PY - 2003/1/7

Y1 - 2003/1/7

N2 - A new series of rigid rod protected and terminal dialkynes with extended π-conjugation through aromatic and hetero-aromatic linker units in the backbone, 2,5-bis(trimethylsilylethynyl)-1-(2-ethylhexyloxy)-4-methoxybenzene la, 2,5-bis(ethynyl)-1-(2-ethylhexyloxy)-4-methoxybenzene 1b, 5,8-bis(trimethylsilylethynyl)quinoline 2a, 5,8-bis(ethynyl)quinoline 2b, 2,3-diphenyl-5,8-bis(trimethylsilylethynyl)quinoxaline 3a, 2,3-diphenyl-5, 8-bis(ethynyl)quinoxaline 3b, 4,7-bis(trimethysilylethynyl)-2,1,3-benzothiadiazole 4a and 4,7-bis(ethynyl)-2,1,3-benzothiadiazole 4b, has been synthesised. Treatment of the complex trans-[Pt(Ph)(Cl)(Et3P)2] with half an equivalent of the diterminal alkynes 1b-4b in iPr 2NH-CH2Cl2, in the presence of CuI, at room temperature, afforded the platinum(II) di-yne complexes trans-[(Et 3P)2(Ph)Pt-C≡C-R-C≡C-Pt(Ph)(Et 3P)2] [R = 1-(2-ethylhexyloxy)-4-methoxybenzene-2,5-diyl 1c, quninoline-5,8-diyl 2c, 2,3-diphenylquinoxaline-5,8-diyl 3c, 2,1,3-benzothiadiazole-4,7-diyl 4c] in good yields. The new acetylide-functionalised ligands and the platinum(II) σ-acetylide complexes have been characterised by analytical and spectroscopic methods and X-ray single crystal structure determinations for 2c-4c. The absorption spectra of the complexes 2c-4c show substantial donor-acceptor interaction between the platinum(II) centres and the conjugated ligands. The photoluminescence spectra of 1c-3c show characteristic singlet (S1) and triplet (T 1) emissions. Both the singlet and triplet emissions as well as the absorption decrease in energy with increasing electronegativity of the spacer groups along the series 1c-4c.

AB - A new series of rigid rod protected and terminal dialkynes with extended π-conjugation through aromatic and hetero-aromatic linker units in the backbone, 2,5-bis(trimethylsilylethynyl)-1-(2-ethylhexyloxy)-4-methoxybenzene la, 2,5-bis(ethynyl)-1-(2-ethylhexyloxy)-4-methoxybenzene 1b, 5,8-bis(trimethylsilylethynyl)quinoline 2a, 5,8-bis(ethynyl)quinoline 2b, 2,3-diphenyl-5,8-bis(trimethylsilylethynyl)quinoxaline 3a, 2,3-diphenyl-5, 8-bis(ethynyl)quinoxaline 3b, 4,7-bis(trimethysilylethynyl)-2,1,3-benzothiadiazole 4a and 4,7-bis(ethynyl)-2,1,3-benzothiadiazole 4b, has been synthesised. Treatment of the complex trans-[Pt(Ph)(Cl)(Et3P)2] with half an equivalent of the diterminal alkynes 1b-4b in iPr 2NH-CH2Cl2, in the presence of CuI, at room temperature, afforded the platinum(II) di-yne complexes trans-[(Et 3P)2(Ph)Pt-C≡C-R-C≡C-Pt(Ph)(Et 3P)2] [R = 1-(2-ethylhexyloxy)-4-methoxybenzene-2,5-diyl 1c, quninoline-5,8-diyl 2c, 2,3-diphenylquinoxaline-5,8-diyl 3c, 2,1,3-benzothiadiazole-4,7-diyl 4c] in good yields. The new acetylide-functionalised ligands and the platinum(II) σ-acetylide complexes have been characterised by analytical and spectroscopic methods and X-ray single crystal structure determinations for 2c-4c. The absorption spectra of the complexes 2c-4c show substantial donor-acceptor interaction between the platinum(II) centres and the conjugated ligands. The photoluminescence spectra of 1c-3c show characteristic singlet (S1) and triplet (T 1) emissions. Both the singlet and triplet emissions as well as the absorption decrease in energy with increasing electronegativity of the spacer groups along the series 1c-4c.

UR - http://www.scopus.com/inward/record.url?scp=18444363856&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=18444363856&partnerID=8YFLogxK

U2 - 10.1039/b208494e

DO - 10.1039/b208494e

M3 - Article

AN - SCOPUS:18444363856

SP - 65

EP - 73

JO - Dalton Transactions

JF - Dalton Transactions

SN - 1477-9226

IS - 1

ER -