title: Dynamics of Re(2,2'-bipyridine)(CO)3Cl MLCT formation and decay after picosecond pulsed X-ray excitation and femtosecond UV excitation.
abstract: The dynamics of Re(2,2'-bipyridine)(CO)3Cl MLCT state formation and decay were determined after femtosecond UV laser excitation and picosecond pulsed X-ray excitation, in an N,N-dimethylformamide (DMF) solution as well as in its solid form. At room temperature, after UV excitation, this MLCT excited state emits both in DMF solution and in the solid form. Transient absorption spectra were measured in solution at various delay times following excitation by a 160 fs, 390 nm laser pulse. There was a prompt absorption increase at around 460 nm occurring within the pump probe convolution (<1 ps), which was assigned to the formation of the 3MLCT state. This transient absorbance was constant over 100 ps. In contrast to the solution state, in the solid state, the emission maximum slightly red-shifts with increasing time after laser excitation. In both solid and solution the emission rises within the system response time. The solid sample exhibited a 1.4 ns emission decay that was not observed for the solution sample. The emission rise from a solid sample after 20 ps pulsed X-ray excitation was significantly slower than the system's time resolution. It is proposed that kinetically energetic electrons are ejected following X-ray induced ionisation, creating ionised tracks in which energetic cations and electrons take time to recombine yielding delayed 3MLCT states that emit.
authors.affiliation: Department of Chemistry, Graduate School of Science, Tohoku University, Sendai, Miyagi, Japan.
authors.forename: Liyan
authors.initials: L
authors.lastname: Zhao
authors.forename: Hideho
authors.initials: H
authors.lastname: Odaka
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Ono
authors.forename: Shinji
authors.initials: S
authors.lastname: Kajimoto
authors.forename: Koji
authors.initials: K
authors.lastname: Hatanaka
authors.forename: Jonathan
authors.initials: J
authors.lastname: Hobley
authors.forename: Hiroshi
authors.initials: H
authors.lastname: Fukumura
mesh_terms: D002248:Carbon Monoxide / Q000737:chemistry; D002712:Chlorides / Q000737:chemistry; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry* / Q000528:radiation effects*; D010777:Photochemistry; D012211:Rhenium / Q000737:chemistry*; D013997:Time Factors; D014466:Ultraviolet Rays; D014965:X-Rays
chemical_list: D002712:Chlorides; D009942:Organometallic Compounds; D012211:Rhenium; D002248:Carbon Monoxide