Ultrafast structural dynamics of Cu(I)-bicinchoninic acid and their implications for solar energy applications

Kelly A. Fransted, Nicholas E. Jackson, Ruifa Zong, Michael W. Mara, Jier Huang, Michael R. Harpham, Megan L. Shelby, Randolph P. Thummel, Lin X. Chen

Research output: Contribution to journalArticlepeer-review


In this study, ultrafast optical transient absorption and X-ray transient absorption (XTA) spectroscopy are used to probe the excited-state dynamics and structural evolution of copper(I) bicinchoninic acid ([Cu(I)-(BCA)2]+), which has similar but less frequently studied biquinoline-based ligands compared to phenanthroline-based complexes. The optical transient absorption measurements performed on the complex in a series of polar protic solvents demonstrate a strong solvent dependency for the excited lifetime, which ranges from approximately 40 ps in water to over 300 ps in 2-methoxyethanol. The XTA experiments showed a reduction of the prominent 1s → 4pz edge peak in the excited-state X-ray absorption nearedge structure (XANES) spectrum, which is indicative of an interaction with a fifth ligand, most likely the solvent. Analysis of the extended X-ray absorption fine structure (EXAFS) spectrum shows a shortening of the metal.ligand bond in the excited state and an increase in the coordination number for the Cu(II) metal center. A flattened structure is supported by DFT calculations that show that the system relaxes into a flattened geometry with a lowest-energy triplet state that has a dipole-forbidden transition to the ground state. While the short excited-state lifetime relative to previously studied Cu(I) diimine complexes could be attributed to this dark triplet state, the strong solvent dependency and the reduction of the 1s → 4pz peak in the XTA data suggest that solvent interaction could also play a role. This detailed study of the dynamics in different solvents provides guidance for modulating excited-state pathways and lifetimes through structural factors such as solvent accessibility to fulfill the excited-state property requirements for efficient light harvesting and electron injection.

Original languageEnglish (US)
Pages (from-to)10497-10506
Number of pages10
JournalJournal of Physical Chemistry A
Issue number45
StatePublished - Nov 13 2014
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry


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