Probing the solvent dependent photophysics of fac-[Re(CO) 3(dppz-X2)Cl] (dppz-X2 = 11,12-X 2-dipyrido[3,2-a:2′,3′-c]phenazine); X = CH3, H, F, Cl, CF3

Marina K. Kuimova, Wassim Z. Alsindi, Alexander J. Blake, E. Stephen Davies, Daniele J. Lampus, Pavel Matousek, Jonathan McMaster, Anthony W. Parker, Michael Towrie, Xue Zhong Sun, Claire Wilson, Michael W. George

Research output: Journal PublicationArticlepeer-review

57 Citations (Scopus)

Abstract

The results of electrochemical measurements, density-functional theory calculations, emission and time -resolved IR (TRIR) spectroscopic studies for fac-[ReCl(CO)3(dppz-X2)], (dppz = dipyrido[3,2-a:2′, 3′-c]phenazine; X = CH3, H, F, Cl, CF3) are reported. For all complexes the calculations show that the lowest unoccupied molecular orbital (LUMO) is a phenazine based orbital localized on the dppz ligand. We observe that three different excited states, IL ππ*, metal-to-ligand charge-transfer (MLCT) (phen), and MLCT (phz), are formed depending upon the substituent on the dppz ligand and on the nature of the solvent. This means that both the energy and the nature of the photophysically active state(s) can be tuned by both chemical modification of dppz ligand and solvent properties. The excited-state dynamics in these systems is directly related to the mechanism of the "light switch effect", and ps-TRIR has allowed a deeper insight into this mechanism by being able to directly monitor the change in the population of the higher lying emissive phen-type 3MLCT and IL ππ* states and the dark 3MLCT (phz) state depending on the different environmental factors.

Original languageEnglish
Pages (from-to)9857-9869
Number of pages13
JournalInorganic Chemistry
Volume47
Issue number21
DOIs
Publication statusPublished - 3 Nov 2008
Externally publishedYes

ASJC Scopus subject areas

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Fingerprint

Dive into the research topics of 'Probing the solvent dependent photophysics of fac-[Re(CO) 3(dppz-X2)Cl] (dppz-X2 = 11,12-X 2-dipyrido[3,2-a:2′,3′-c]phenazine); X = CH3, H, F, Cl, CF3'. Together they form a unique fingerprint.

Cite this