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

Research output: Contribution to journalArticlepeer-review

68 Scopus citations


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.

Original languageEnglish (US)
Pages (from-to)14521-14527
Number of pages7
JournalJournal of Physical Chemistry B
Issue number45
StatePublished - Dec 8 2010

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films
  • Materials Chemistry


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