title: π donation and its effects on the excited-state lifetimes of luminescent platinum(II) terpyridine complexes in solution.
abstract: Introducing electron-donating groups extends the excited-state lifetimes of platinum(II)-terpyridine complexes in fluid solution. Such systems are of interest for a variety of applications, viz., as DNA-binding agents or as components in luminescence-based devices, especially sensors. The complexes investigated here are of the form [Pt(4'-X-T)Y](+), where 4'-X-T denotes a 4'-substituted 2,2':6',2″-terpyridine ligand and Y denotes the coligand. The π-donating abilities of -X and -Y increase systematically in the orders -NHMe < -NMe2 < -(pyrrolidin-1-yl) and -CN < -Cl < -CCPh, respectively. The results presented include crystal structures of two new 4'-NHMe-T complexes of platinum, as well as absorption, emission, and excited-state lifetime data for nine complexes. Excited-state lifetimes obtained in deoxygenated dichloromethane vary by a factor of 100, ranging from 24 μs for [Pt(4'-pyrr-T)CN](+) to 0.24 μs for [Pt(4'-ma-T)Cl](+), where ma-T denotes 4'-(methylamino)-2,2':6',2″-terpyridine and pyrr-T denotes 4'-(pyrrolidin-1-yl)-2,2':6',2″-terpyridine. Analysis of experimental and computational results shows that introducing a simple amine group on the terpyridine and/or a π-donating coligand engenders the emitting state with intraligand charge-transfer (ILCT) and/or ligand-ligand charge-transfer (LLCT) character. The excited-state lifetime increases when the change in orbital parentage lowers the emission energy, suppresses quenching via d-d states, and encourages delocalization of the excitation onto the ligand(s). At some point, however, the energy is low enough that direct vibronic coupling to the ground-state surface becomes important, and the lifetime begins to decrease again.
authors.affiliation: Department of Chemistry, 560 Oval Drive, Purdue University, West Lafayette, Indiana 47907-2084, United States.
authors.forename: Lauren M
authors.initials: LM
authors.lastname: Hight
authors.forename: Meaghan C
authors.initials: MC
authors.lastname: McGuire
authors.forename: Yu
authors.initials: Y
authors.lastname: Zhang
authors.forename: Matthew A
authors.initials: MA
authors.lastname: Bork
authors.forename: Phillip E
authors.initials: PE
authors.lastname: Fanwick
authors.forename: Adam
authors.initials: A
authors.lastname: Wasserman
authors.forename: David R
authors.initials: DR
authors.lastname: McMillin