Interrogating conformationally dependent electron-transfer dynamics via ultrafast visible pump/IR probe spectroscopy.

Journal Article (Journal Article)

We demonstrate for the first time the utility of time-resolved visible pump/mid-infrared (IR) probe spectroscopy to interrogate directly, and provide unique infomation regarding, conformationally dependent photoinduced ET dynamics and the subsequent structural evolution of the resulting charge-separated (CS) state. Exemplary polarized visible pump/IR probe experiments involving N-[5-(10,20-diphenylporphinato)zinc(II)]-N'(octyl)pyromellitic diimide (PZn-PI) and [5-[4'-(N-(N'-octyl)pyromellitic diimide)phenyl)ethynyl]-10,20-diphenylporphinato]zinc(II) (PZn()PI) show that it is possible to assess the mean PZn-to-PI interplanar torsional angle of electronically excited structural conformers that undergo ET within the sub-ps time domain for both of these donor-spacer-acceptor (D-Sp-A) systems. Further transient specroscopic experiments carried out on PZn()PI determine how this angle evolves with time. Because vibrational transition moments are often known and typically localized, this work underscores that polarized visible pump/IR probe spectroscopy defines a valuable tool to interrogate structrure in both electronically excited and CS states; this fact, coupled with the ultrafast time resolution and high senseitivity offered by this technique, make it ideally suited to probe a range of mechanistic issues relevant to charge-transfer reactions.

Full Text

Duke Authors

Cited Authors

  • Rubtsov, IV; Redmore, NP; Hochstrasser, RM; Therien, MJ

Published Date

  • March 2004

Published In

Volume / Issue

  • 126 / 9

Start / End Page

  • 2684 - 2685

PubMed ID

  • 14995169

Electronic International Standard Serial Number (EISSN)

  • 1520-5126

International Standard Serial Number (ISSN)

  • 0002-7863

Digital Object Identifier (DOI)

  • 10.1021/ja0305499


  • eng