Synthesis, characterisation and theoretical study of ruthenium 4,4′-bi-1,2,3-triazolyl complexes: Fundamental switching of the nature of S 1 and T 1 states from MLCT to MC

Christine E. Welby, Stev Grkinic, Adam Zahid, Baljinder S. Uppal, Elizabeth A. Gibson, Craig R. Rice, Paul I.P. Elliott

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Abstract

The series of complexes [Ru(bpy) 3-n(btz) n][PF 6] 2 (bpy = 2,2′-bipyridyl, btz = 1,1′-dibenzyl-4,4′-bi-1,2,3-triazolyl, 2n = 1, 3n = 2, 4n = 3) have been prepared and characterised, and the photophysical and electronic effects imparted by the btz ligand were investigated. Complexes 2 and 3 exhibit MLCT absorption bands at 425 and 446 nm respectively showing a progressive blue-shift in the absorption on increasing the btz ligand content when compared to [Ru(bpy) 3][Cl] 2 (1). Complex 4 exhibits a heavily blue-shifted absorption spectrum with respect to those of 1-3, indicating that the LUMO of the latter are bpy-centred with little or no btz contribution whereas that of 4 is necessarily btz-centred. DFT calculations on analogous complexes 1′-4′ (in which the benzyl substituents are replaced by methyl) show that the HOMO-LUMO gap increases by 0.3 eV from 1′-3′ through destabilisation of the LUMO with respect to the HOMO. The HOMO-LUMO gap of 4′ increases by 0.98 eV compared to that of 3′ due to significant destabilisation of the LUMO. Examination of TDDFT data show that the S 1 states of 1′-3′ are 1MLCT in character whereas that of 4′ is 1MC. The optimisation of the T 1 state of 4′ leads to the elongation of two mutually trans Ru-N bonds to yield [Ru(κ 2-btz)(κ 1-btz) 2] 2+, confirming the 3MC character. Thus, replacement of bpy by btz leads to a fundamental change in the ordering of excited states such that the nature of the lowest energy excited state changes from MLCT in nature to MC.

LanguageEnglish
Pages7637-7646
Number of pages10
JournalDalton Transactions
Volume41
Issue number25
DOIs
Publication statusPublished - 7 Jul 2012

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Ruthenium
Excited states
Absorption spectra
Ligands
2,2'-Dipyridyl
Discrete Fourier transforms
Elongation
tris(2,2'-bipyridine)ruthenium II
dichlorotetrakis(dimethyl sulfoxide)ruthenium II

Cite this

@article{52fc9d4d8b3b43009e114c8ef51e5128,
title = "Synthesis, characterisation and theoretical study of ruthenium 4,4′-bi-1,2,3-triazolyl complexes: Fundamental switching of the nature of S 1 and T 1 states from MLCT to MC",
abstract = "The series of complexes [Ru(bpy) 3-n(btz) n][PF 6] 2 (bpy = 2,2′-bipyridyl, btz = 1,1′-dibenzyl-4,4′-bi-1,2,3-triazolyl, 2n = 1, 3n = 2, 4n = 3) have been prepared and characterised, and the photophysical and electronic effects imparted by the btz ligand were investigated. Complexes 2 and 3 exhibit MLCT absorption bands at 425 and 446 nm respectively showing a progressive blue-shift in the absorption on increasing the btz ligand content when compared to [Ru(bpy) 3][Cl] 2 (1). Complex 4 exhibits a heavily blue-shifted absorption spectrum with respect to those of 1-3, indicating that the LUMO of the latter are bpy-centred with little or no btz contribution whereas that of 4 is necessarily btz-centred. DFT calculations on analogous complexes 1′-4′ (in which the benzyl substituents are replaced by methyl) show that the HOMO-LUMO gap increases by 0.3 eV from 1′-3′ through destabilisation of the LUMO with respect to the HOMO. The HOMO-LUMO gap of 4′ increases by 0.98 eV compared to that of 3′ due to significant destabilisation of the LUMO. Examination of TDDFT data show that the S 1 states of 1′-3′ are 1MLCT in character whereas that of 4′ is 1MC. The optimisation of the T 1 state of 4′ leads to the elongation of two mutually trans Ru-N bonds to yield [Ru(κ 2-btz)(κ 1-btz) 2] 2+, confirming the 3MC character. Thus, replacement of bpy by btz leads to a fundamental change in the ordering of excited states such that the nature of the lowest energy excited state changes from MLCT in nature to MC.",
author = "Welby, {Christine E.} and Stev Grkinic and Adam Zahid and Uppal, {Baljinder S.} and Gibson, {Elizabeth A.} and Rice, {Craig R.} and Elliott, {Paul I.P.}",
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Synthesis, characterisation and theoretical study of ruthenium 4,4′-bi-1,2,3-triazolyl complexes : Fundamental switching of the nature of S 1 and T 1 states from MLCT to MC. / Welby, Christine E.; Grkinic, Stev; Zahid, Adam; Uppal, Baljinder S.; Gibson, Elizabeth A.; Rice, Craig R.; Elliott, Paul I.P.

In: Dalton Transactions, Vol. 41, No. 25, 07.07.2012, p. 7637-7646.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis, characterisation and theoretical study of ruthenium 4,4′-bi-1,2,3-triazolyl complexes

T2 - Dalton Transactions

AU - Welby, Christine E.

AU - Grkinic, Stev

AU - Zahid, Adam

AU - Uppal, Baljinder S.

AU - Gibson, Elizabeth A.

AU - Rice, Craig R.

AU - Elliott, Paul I.P.

PY - 2012/7/7

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N2 - The series of complexes [Ru(bpy) 3-n(btz) n][PF 6] 2 (bpy = 2,2′-bipyridyl, btz = 1,1′-dibenzyl-4,4′-bi-1,2,3-triazolyl, 2n = 1, 3n = 2, 4n = 3) have been prepared and characterised, and the photophysical and electronic effects imparted by the btz ligand were investigated. Complexes 2 and 3 exhibit MLCT absorption bands at 425 and 446 nm respectively showing a progressive blue-shift in the absorption on increasing the btz ligand content when compared to [Ru(bpy) 3][Cl] 2 (1). Complex 4 exhibits a heavily blue-shifted absorption spectrum with respect to those of 1-3, indicating that the LUMO of the latter are bpy-centred with little or no btz contribution whereas that of 4 is necessarily btz-centred. DFT calculations on analogous complexes 1′-4′ (in which the benzyl substituents are replaced by methyl) show that the HOMO-LUMO gap increases by 0.3 eV from 1′-3′ through destabilisation of the LUMO with respect to the HOMO. The HOMO-LUMO gap of 4′ increases by 0.98 eV compared to that of 3′ due to significant destabilisation of the LUMO. Examination of TDDFT data show that the S 1 states of 1′-3′ are 1MLCT in character whereas that of 4′ is 1MC. The optimisation of the T 1 state of 4′ leads to the elongation of two mutually trans Ru-N bonds to yield [Ru(κ 2-btz)(κ 1-btz) 2] 2+, confirming the 3MC character. Thus, replacement of bpy by btz leads to a fundamental change in the ordering of excited states such that the nature of the lowest energy excited state changes from MLCT in nature to MC.

AB - The series of complexes [Ru(bpy) 3-n(btz) n][PF 6] 2 (bpy = 2,2′-bipyridyl, btz = 1,1′-dibenzyl-4,4′-bi-1,2,3-triazolyl, 2n = 1, 3n = 2, 4n = 3) have been prepared and characterised, and the photophysical and electronic effects imparted by the btz ligand were investigated. Complexes 2 and 3 exhibit MLCT absorption bands at 425 and 446 nm respectively showing a progressive blue-shift in the absorption on increasing the btz ligand content when compared to [Ru(bpy) 3][Cl] 2 (1). Complex 4 exhibits a heavily blue-shifted absorption spectrum with respect to those of 1-3, indicating that the LUMO of the latter are bpy-centred with little or no btz contribution whereas that of 4 is necessarily btz-centred. DFT calculations on analogous complexes 1′-4′ (in which the benzyl substituents are replaced by methyl) show that the HOMO-LUMO gap increases by 0.3 eV from 1′-3′ through destabilisation of the LUMO with respect to the HOMO. The HOMO-LUMO gap of 4′ increases by 0.98 eV compared to that of 3′ due to significant destabilisation of the LUMO. Examination of TDDFT data show that the S 1 states of 1′-3′ are 1MLCT in character whereas that of 4′ is 1MC. The optimisation of the T 1 state of 4′ leads to the elongation of two mutually trans Ru-N bonds to yield [Ru(κ 2-btz)(κ 1-btz) 2] 2+, confirming the 3MC character. Thus, replacement of bpy by btz leads to a fundamental change in the ordering of excited states such that the nature of the lowest energy excited state changes from MLCT in nature to MC.

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U2 - 10.1039/c2dt30510k

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