title: Photophysics in platinum(II) bipyridylacetylides.
abstract: The synthesis, structural characterization, photoluminescence, and excited state absorption properties of a series of platinum(II) terpyridyl complexes bearing a bipyridyl acetylide subunit are presented. The [(t)Bu(3)tpyPtC identical withCbpy](+) (1) complex displays a broad and structureless emission profile at room temperature (RT), a lifetime of 5.8 mus, and transient absorption (TA) difference spectra characteristic of a charge transfer (CT) excited state. Upon coordination of Fe(2+) to 1, producing tetranuclear 2, the CT emission was quantitatively quenched presumably through the low-lying iron-based ligand field states present. Surprisingly, the addition of Zn(2+) to solutions of 1 produces a higher energy emissive state with a substantially longer excited state lifetime of 16.1 mus. The combined spectroscopic data measured for the zinc titration product (3) suggests that the overall excited state is dominated by a CT manifold, albeit at higher energy relative to 1. The photophysics of a bis-phosphine complex bearing two trans-disposed bpy-acetylide subunits (4) produced a model chromophore possessing an intraligand triplet excited state with a lifetime of 26 mus at RT. The bipyridyl analogue of 1, (t)Bu(2)bpyPt(C identical withCbpy)(2) (5), was also prepared and its photophysics are consistent with a lowest CT parentage at RT. The 77 K emission spectra measured for complexes 1, 3, 4, and 5 are all consistent with a triplet bpy-acetylide localized excited state; the E(00) energies vary over a modest 344 cm(-1) across the series. However, the shorter 77 K excited state lifetimes observed for 1, 3, and 5 in comparison to 4 suggests that the energetically proximate CT state in the former compounds significantly influences excited state decay at low temperature.
authors.affiliation: Department of Chemistry and Center for Photochemical Sciences, Bowling Green State University, Bowling Green, Ohio 43403, USA.
authors.forename: Maria L
authors.initials: ML
authors.lastname: Muro
authors.forename: Stéphane
authors.initials: S
authors.lastname: Diring
authors.forename: Xianghuai
authors.initials: X
authors.lastname: Wang
authors.forename: Raymond
authors.initials: R
authors.lastname: Ziessel
authors.forename: Felix N
authors.initials: FN
authors.lastname: Castellano
mesh_terms: D000480:Alkynes / Q000737:chemistry*; D049449:Luminescence; D015394:Molecular Structure; D009944:Organoplatinum Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010777:Photochemistry; D011725:Pyridines / Q000737:chemistry*; D013696:Temperature; D015032:Zinc / Q000737:chemistry
chemical_list: D000480:Alkynes; D009944:Organoplatinum Compounds; D011725:Pyridines; D015032:Zinc