Abstract
Although they were discovered almost four decades ago, Cu(I) diimine complexes have emerged as a group of transition metal complexes that can play important roles in solar energy conversion and utilization, and have potential to replace the quintessential ruthenium polypyridyl complexes as light sensitizers, electron donors and catalytic centers. This review includes some recent photophysical studies and transient structural studies of Cu(I) diimine complexes using ultrafast optical transient absorption and emission as well as X-ray transient absorption spectroscopy. The main focus is on identifying the key structural factors that influence the excited-state properties, such as structural reorganization, intersystem crossing and solvent quenching, with these relatively new techniques on the ultrafast time scales. Ultimately, these structural factors can be used to rationally control the energetics and dynamics of the MLCT state during the light conversion processes. This insight will serve as guidance for material design using Cu(I) diimine complexes as building blocks.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 2-18 |
| Number of pages | 17 |
| Journal | Coordination Chemistry Reviews |
| Volume | 282-283 |
| DOIs | |
| State | Published - Jan 1 2015 |
Funding
We thank the support from the U.S. Department of Energy , Office of Science , Office of Basic Energy Sciences , under Contract No. DE-AC02-06CH11357. Use of the Advanced Photon Source at Argonne National Laboratory was supported by the U. S. Department of Energy, Office of Science, Office of Basic Energy Sciences, under Contract No. DE-AC02-06CH11357. The authors would like to thank Drs. Klaus Attenkofer (now at NSLS-II, Brookhaven National Laboratory), Guy Jennings, Xiaoyi Zhang and Mr. Charles Kurtz of the Advanced Photon Source for their contributions to the Beamline 11ID-D facility at the APS. LXC would like to thank her collaborators in the XTA team since 2002, Drs. G. B. Shaw, E. C. Wasinger, J. V. Lockard, M. R. Harpham, A. B. Stickrath, J. Huang, Ms. M. L. Shelby for their contributions to the results included in the review. Our other collaborators contributions and scientific exchanges are also appreciated, Drs. G. Smolentsev, Kristoffer M. Haldrup, Profs. A. Sotadov, G. J. Meyer, F. Castellano, P. Coppens, and many others. The instrumentation supports (to LXC et al.) from the US Department of Energy for purchasing lasers, detectors and other related equipment enabling the initiation and upgrade of XTA experiments at Beamline 11IDD are greatly appreciated.
Keywords
- Copper diimine
- Excited state structure
- Solar energy conversion
- Transition metal complexes
- Ultrafast X-ray absorption
- Ultrafast optical transient absorption
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry
- Materials Chemistry