TY - JOUR
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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U2 - 10.1021/jp102278u
DO - 10.1021/jp102278u
M3 - Article
C2 - 20666433
AN - SCOPUS:78650099802
SN - 1520-6106
VL - 114
SP - 14521
EP - 14527
JO - Journal of Physical Chemistry B
JF - Journal of Physical Chemistry B
IS - 45
ER -