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Influence of Ligand Substitution on Excited State Structural Dynamics in Cu(I) Bisphenanthroline Complexes

Lockard, Jenny V; Kabehie, Sanaz; Zink, Jeffrey I; Smolentsev, Grigory LU ; Soldatov, Alexander and Chen, Lin X (2010) In The Journal of Physical Chemistry Part B 114(45). p.14521-14527
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)bis(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.... (More)
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)bis(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. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part B
volume
114
issue
45
pages
14521 - 14527
publisher
The American Chemical Society
external identifiers
  • wos:000284018000049
  • pmid:20666433
  • scopus:78650099802
ISSN
1520-5207
DOI
10.1021/jp102278u
language
English
LU publication?
yes
id
974f89b9-a01e-45ad-9c7d-ed7cf853ff9a (old id 1644481)
date added to LUP
2010-08-31 09:07:51
date last changed
2018-05-29 11:40:17
@article{974f89b9-a01e-45ad-9c7d-ed7cf853ff9a,
  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)bis(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.},
  author       = {Lockard, Jenny V and Kabehie, Sanaz and Zink, Jeffrey I and Smolentsev, Grigory and Soldatov, Alexander and Chen, Lin X},
  issn         = {1520-5207},
  language     = {eng},
  number       = {45},
  pages        = {14521--14527},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part B},
  title        = {Influence of Ligand Substitution on Excited State Structural Dynamics in Cu(I) Bisphenanthroline Complexes},
  url          = {http://dx.doi.org/10.1021/jp102278u},
  volume       = {114},
  year         = {2010},
}