title: Triplet Energy Transport in Platinum-Acetylide Light Harvesting Arrays.
abstract: Light harvesting and triplet energy transport is investigated in chromophore-functionalized polystyrene polymers featuring light harvesting and energy acceptor chromophores (traps) at varying loading. The series of precision polymers was constructed via reversible addition-fragmentation transfer polymerization and functionalized with platinum acetylide triplet chromophores by using an azide-alkyne "click" reaction. The polymers have narrow polydispersity and degree of polymerization ∼60. The chromophores have the general structure, trans-[-R-C6H4-C≡C-Pt(PBu3)2-C≡C-Ar], where R is the attachment point to the polystyrene backbone and Ar is either -C6H4-C≡C-Ph or -pyrenyl (PE2-Pt and Py-Pt, respectively, with triplet energies of 2.35 and 1.88 eV). The polychromophores contain mainly the high-energy PE2-Pt units (light absorber and energy donor), with randomly distributed Py-Pt units (3-20% loading, energy acceptor). Photophysical methods are used to study the dynamics and efficiency of energy transport from the PE2-Pt to Py-Pt units in the polychromophores. The energy transfer efficiency is >90% for copolymers that contain 5% of the Py-Pt acceptor units. Time-resolved phosphorescence measurements combined with Monte Carlo exciton dynamics simulations suggest that the mechanism of exciton transport is exchange energy transfer hopping between PE2-Pt units.
authors.affiliation: †Department of Chemistry and Center for Macromolecular Science and Engineering and ‡Department of Chemical Engineering, University of Florida, P.O. Box 117200, Gainesville, Florida 32611-7200, United States.
authors.forename: Zhuo
authors.initials: Z
authors.lastname: Chen
authors.affiliation: †Department of Chemistry and Center for Macromolecular Science and Engineering and ‡Department of Chemical Engineering, University of Florida, P.O. Box 117200, Gainesville, Florida 32611-7200, United States.
authors.forename: Hsien-Yi
authors.initials: HY
authors.lastname: Hsu
authors.affiliation: †Department of Chemistry and Center for Macromolecular Science and Engineering and ‡Department of Chemical Engineering, University of Florida, P.O. Box 117200, Gainesville, Florida 32611-7200, United States.
authors.forename: Mert
authors.initials: M
authors.lastname: Arca
authors.affiliation: †Department of Chemistry and Center for Macromolecular Science and Engineering and ‡Department of Chemical Engineering, University of Florida, P.O. Box 117200, Gainesville, Florida 32611-7200, United States.
authors.forename: Kirk S
authors.initials: KS
authors.lastname: Schanze