title: Facile synthesis, structure, and luminescence properties of Pt(diimine)bis(arylacetylide) chromophore-donor dyads.
abstract: The luminescent complex Pt(dpphen)bis(arylacetylide) complex (1) (dpphen = 4,7-diphenylphenanthroline and arylacetylide = 4-ethynylbenzaldehyde) has been synthesized and characterized structurally and spectroscopically. Complex 1 has been employed in the synthesis of donor-chromophore (D-C) dyads through Schiff base condensations of different anilines to give imine-linked dyads 2-4 and through imine reduction with borohydride, to give the corresponding amine-linked dyads 2a-4a. Crystal structure determinations of 1-4 and 4a establish a distorted square-planar geometry around the Pt(II) ion in each system with cis arylacetylide ligands and a diimine-constrained N-Pt-N bond angle of ca. 79.5 degrees. Complex 1 is strongly emissive having a relative quantum yield (phi) of 36% and an excited-state lifetime of 3.1 micros. In accord with the notion of photoinduced electron transfer from the aniline-based donor to the photoexcited chromophore, the emission of dyads 2-4 and 2a-4a is effectively quenched in all solvents tested. The intense absorption at 400 nm (30000-70000 L/mol.cm) for 2 and 2a has been assigned as an intraligand pi-pi* transition, whereas the lowest-energy transitions for all other dyads correspond to Pt-to-pi(diimine) MLCT transitions. Although the dyads can be synthesized in a facile manner, photolysis experiments reveal that both the imine and amine linkages are photochemically unstable, resulting in hydrolysis and regeneration of the aldehyde-containing chromophore 1.
authors.affiliation: Department of Chemistry, University of Rochester, Rochester, New York 14627, USA.
authors.forename: Thaddeus J
authors.initials: TJ
authors.lastname: Wadas
authors.forename: Soma
authors.initials: S
authors.lastname: Chakraborty
authors.forename: Rene J
authors.initials: RJ
authors.lastname: Lachicotte
authors.forename: Quan-Ming
authors.initials: QM
authors.lastname: Wang
authors.forename: Richard
authors.initials: R
authors.lastname: Eisenberg