Dinuclear Diphosphine Complexes of Gold(I) Alkynyls, the Effects of Alkynyl Substituents onto Photophysical Behavior

Julia R. Shakirova, Masaki Shimada, Dmitrii A. Olisov, Galina L. Starova, Hiroshi Nishihara, Sergey P. Tunik

Research output

Abstract

A series of dinuclear diphosphine complexes of gold(I) alkynyls containing bis(diphenylphosphanyl)ethane/propane and alkynyl ligands with aromatic substituents (biphenyl, pyrene, and azobenzene) was synthesized and characterized using X-ray crystallography and NMR spectroscopy. Photophysical parameters of the compounds obtained strongly depend on the nature of aromatic substituents in the alkynyl ligands. Azobenzene containing derivatives are non-luminescent, whereas biphenyl and pyrene containing complexes display moderate emission both in solution and in solid state. The complexes with biphenyl substituents display strong heavy atom effect and show typical phosphorescent emission. In contrast, the complexes containing pyrene chromophore are fluorescent that points to the absence of spin orbit coupling in these systems, which additionally display static excimer emission in solid phase due to ground state π-stacking of the pyrene moieties.

Original languageEnglish
Pages (from-to)308-316
Number of pages9
JournalZeitschrift fur Anorganische und Allgemeine Chemie
Volume644
Issue number5
DOIs
Publication statusPublished - 15 Mar 2018

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Gold
Ligands
Propane
Ethane
X ray crystallography
Chromophores
Ground state
Nuclear magnetic resonance spectroscopy
Orbits
Derivatives
Atoms
pyrene
diphenyl
azobenzene

Scopus subject areas

  • Inorganic Chemistry

Cite this

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title = "Dinuclear Diphosphine Complexes of Gold(I) Alkynyls, the Effects of Alkynyl Substituents onto Photophysical Behavior",
abstract = "A series of dinuclear diphosphine complexes of gold(I) alkynyls containing bis(diphenylphosphanyl)ethane/propane and alkynyl ligands with aromatic substituents (biphenyl, pyrene, and azobenzene) was synthesized and characterized using X-ray crystallography and NMR spectroscopy. Photophysical parameters of the compounds obtained strongly depend on the nature of aromatic substituents in the alkynyl ligands. Azobenzene containing derivatives are non-luminescent, whereas biphenyl and pyrene containing complexes display moderate emission both in solution and in solid state. The complexes with biphenyl substituents display strong heavy atom effect and show typical phosphorescent emission. In contrast, the complexes containing pyrene chromophore are fluorescent that points to the absence of spin orbit coupling in these systems, which additionally display static excimer emission in solid phase due to ground state π-stacking of the pyrene moieties.",
keywords = "Aurophilic interactions, Excimer emission, Fluorescence, Gold, Phosphorescence",
author = "Shakirova, {Julia R.} and Masaki Shimada and Olisov, {Dmitrii A.} and Starova, {Galina L.} and Hiroshi Nishihara and Tunik, {Sergey P.}",
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language = "English",
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TY - JOUR

T1 - Dinuclear Diphosphine Complexes of Gold(I) Alkynyls, the Effects of Alkynyl Substituents onto Photophysical Behavior

AU - Shakirova, Julia R.

AU - Shimada, Masaki

AU - Olisov, Dmitrii A.

AU - Starova, Galina L.

AU - Nishihara, Hiroshi

AU - Tunik, Sergey P.

PY - 2018/3/15

Y1 - 2018/3/15

N2 - A series of dinuclear diphosphine complexes of gold(I) alkynyls containing bis(diphenylphosphanyl)ethane/propane and alkynyl ligands with aromatic substituents (biphenyl, pyrene, and azobenzene) was synthesized and characterized using X-ray crystallography and NMR spectroscopy. Photophysical parameters of the compounds obtained strongly depend on the nature of aromatic substituents in the alkynyl ligands. Azobenzene containing derivatives are non-luminescent, whereas biphenyl and pyrene containing complexes display moderate emission both in solution and in solid state. The complexes with biphenyl substituents display strong heavy atom effect and show typical phosphorescent emission. In contrast, the complexes containing pyrene chromophore are fluorescent that points to the absence of spin orbit coupling in these systems, which additionally display static excimer emission in solid phase due to ground state π-stacking of the pyrene moieties.

AB - A series of dinuclear diphosphine complexes of gold(I) alkynyls containing bis(diphenylphosphanyl)ethane/propane and alkynyl ligands with aromatic substituents (biphenyl, pyrene, and azobenzene) was synthesized and characterized using X-ray crystallography and NMR spectroscopy. Photophysical parameters of the compounds obtained strongly depend on the nature of aromatic substituents in the alkynyl ligands. Azobenzene containing derivatives are non-luminescent, whereas biphenyl and pyrene containing complexes display moderate emission both in solution and in solid state. The complexes with biphenyl substituents display strong heavy atom effect and show typical phosphorescent emission. In contrast, the complexes containing pyrene chromophore are fluorescent that points to the absence of spin orbit coupling in these systems, which additionally display static excimer emission in solid phase due to ground state π-stacking of the pyrene moieties.

KW - Aurophilic interactions

KW - Excimer emission

KW - Fluorescence

KW - Gold

KW - Phosphorescence

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U2 - 10.1002/zaac.201700415

DO - 10.1002/zaac.201700415

M3 - Article

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VL - 644

SP - 308

EP - 316

JO - Zeitschrift fur Anorganische und Allgemeine Chemie

JF - Zeitschrift fur Anorganische und Allgemeine Chemie

SN - 0044-2313

IS - 5

ER -