Influence of ligand substitution on excited state structural dynamics in Cu(I) bisphenanthroline complexes

Jenny V. Lockard; Sanaz Kabehie; Jeffrey I. Zink; Grigory Smolentsev; Alexander Soldatov; Lin X. Chen

doi:10.1021/jp102278u

Influence of ligand substitution on excited state structural dynamics in Cu(I) bisphenanthroline complexes

Jenny V. Lockard, Sanaz Kabehie, Jeffrey I. Zink, Grigory Smolentsev, Alexander Soldatov, Lin X. Chen

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Abstract

This study explores the influences of steric hindrance and excited state solvent ligation on the excited state dynamics of Cu^I diimine complexes. Ultrafast excited state dynamics of Cu(I)bis(3,8-di(ethynyltrityl)-1, 10-phenanthroline) [Cu^I(detp)₂]⁺ are measured using femtosecond transient absorption spectroscopy. The steady state electronic absorption spectra and measured lifetimes are compared to those of Cu(I)Ms(1,10-phenanthroline), [Cu^I(phen)₂]⁺, and Cu(I)bis(2-9-dimethyl-1,10-phenanthroline), [Cu^I(dmp) ₂]⁺, model complexes to determine the influence of different substitution patterns of the phenanthroline ligand on the structural dynamics associated with the metal to ligand charge transfer excited states. Similarities between the [Cu^I(detp)₂]⁺ and [Cu^I(phen)₂]⁺ excited state lifetimes were observed in both coordinating and noncoordinating solvents and attributed to the lack of steric hindrance from substitution at the 2- and 9-positions. The solution-phase X-ray absorption spectra of [Cu^I(detp) ₂]⁺, [Cu^I(phen)₂]⁺, and [Cu^I(dmp)₂]⁺ are reported along with finite difference method calculations that are used to determine the degree of ground state dihedral angle distortion in solution and to account for the pre-edge features observed in the XANES region.

Original language	English (US)
Pages (from-to)	14521-14527
Number of pages	7
Journal	Journal of Physical Chemistry B
Volume	114
Issue number	45
DOIs	https://doi.org/10.1021/jp102278u
State	Published - Dec 8 2010
Externally published	Yes

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Surfaces, Coatings and Films
Materials Chemistry

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title = "Influence of ligand substitution on excited state structural dynamics in Cu(I) bisphenanthroline complexes",

abstract = "This study explores the influences of steric hindrance and excited state solvent ligation on the excited state dynamics of CuI diimine complexes. Ultrafast excited state dynamics of Cu(I)bis(3,8-di(ethynyltrityl)-1, 10-phenanthroline) [CuI(detp)2]+ are measured using femtosecond transient absorption spectroscopy. The steady state electronic absorption spectra and measured lifetimes are compared to those of Cu(I)Ms(1,10-phenanthroline), [CuI(phen)2]+, and Cu(I)bis(2-9-dimethyl-1,10-phenanthroline), [CuI(dmp) 2]+, model complexes to determine the influence of different substitution patterns of the phenanthroline ligand on the structural dynamics associated with the metal to ligand charge transfer excited states. Similarities between the [CuI(detp)2]+ and [CuI(phen)2]+ excited state lifetimes were observed in both coordinating and noncoordinating solvents and attributed to the lack of steric hindrance from substitution at the 2- and 9-positions. The solution-phase X-ray absorption spectra of [CuI(detp) 2]+, [CuI(phen)2]+, and [CuI(dmp)2]+ are reported along with finite difference method calculations that are used to determine the degree of ground state dihedral angle distortion in solution and to account for the pre-edge features observed in the XANES region.",

author = "Lockard, {Jenny V.} and Sanaz Kabehie and Zink, {Jeffrey I.} and Grigory Smolentsev and Alexander Soldatov and Chen, {Lin X.}",

year = "2010",

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T1 - Influence of ligand substitution on excited state structural dynamics in Cu(I) bisphenanthroline complexes

AU - Lockard, Jenny V.

AU - Kabehie, Sanaz

AU - Zink, Jeffrey I.

AU - Smolentsev, Grigory

AU - Soldatov, Alexander

AU - Chen, Lin X.

PY - 2010/12/8

Y1 - 2010/12/8

N2 - This study explores the influences of steric hindrance and excited state solvent ligation on the excited state dynamics of CuI diimine complexes. Ultrafast excited state dynamics of Cu(I)bis(3,8-di(ethynyltrityl)-1, 10-phenanthroline) [CuI(detp)2]+ are measured using femtosecond transient absorption spectroscopy. The steady state electronic absorption spectra and measured lifetimes are compared to those of Cu(I)Ms(1,10-phenanthroline), [CuI(phen)2]+, and Cu(I)bis(2-9-dimethyl-1,10-phenanthroline), [CuI(dmp) 2]+, model complexes to determine the influence of different substitution patterns of the phenanthroline ligand on the structural dynamics associated with the metal to ligand charge transfer excited states. Similarities between the [CuI(detp)2]+ and [CuI(phen)2]+ excited state lifetimes were observed in both coordinating and noncoordinating solvents and attributed to the lack of steric hindrance from substitution at the 2- and 9-positions. The solution-phase X-ray absorption spectra of [CuI(detp) 2]+, [CuI(phen)2]+, and [CuI(dmp)2]+ are reported along with finite difference method calculations that are used to determine the degree of ground state dihedral angle distortion in solution and to account for the pre-edge features observed in the XANES region.

AB - This study explores the influences of steric hindrance and excited state solvent ligation on the excited state dynamics of CuI diimine complexes. Ultrafast excited state dynamics of Cu(I)bis(3,8-di(ethynyltrityl)-1, 10-phenanthroline) [CuI(detp)2]+ are measured using femtosecond transient absorption spectroscopy. The steady state electronic absorption spectra and measured lifetimes are compared to those of Cu(I)Ms(1,10-phenanthroline), [CuI(phen)2]+, and Cu(I)bis(2-9-dimethyl-1,10-phenanthroline), [CuI(dmp) 2]+, model complexes to determine the influence of different substitution patterns of the phenanthroline ligand on the structural dynamics associated with the metal to ligand charge transfer excited states. Similarities between the [CuI(detp)2]+ and [CuI(phen)2]+ excited state lifetimes were observed in both coordinating and noncoordinating solvents and attributed to the lack of steric hindrance from substitution at the 2- and 9-positions. The solution-phase X-ray absorption spectra of [CuI(detp) 2]+, [CuI(phen)2]+, and [CuI(dmp)2]+ are reported along with finite difference method calculations that are used to determine the degree of ground state dihedral angle distortion in solution and to account for the pre-edge features observed in the XANES region.

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Influence of ligand substitution on excited state structural dynamics in Cu(I) bisphenanthroline complexes

Abstract

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