Triplet Energy Transport in Platinum-Acetylide Light Harvesting Arrays

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• 作者：Zhuo Chen ; Hsien-Yi Hsu ; Mert Arca ; Kirk S. Schanze
• 刊名：Journal of Physical Chemistry B
• 出版年：2015
• 出版时间：June 18, 2015
• 年：2015
• 卷：119
• 期：24
• 页码：7198-7209
• 全文大小：598K
• ISSN：1520-5207

文摘

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鈥揻ragmentation transfer polymerization and functionalized with platinum acetylide triplet chromophores by using an azide鈥揳lkyne 鈥渃lick鈥?reaction. The polymers have narrow polydispersity and degree of polymerization 鈭?0. The chromophores have the general structure, trans-[鈭扲鈥揅₆H₄鈥揅鈮鈥揚t(PBu₃)₂鈥揅鈮鈥揂r], where R is the attachment point to the polystyrene backbone and Ar is either 鈥揅₆H₄鈥揅鈮鈥揚h or 鈥損yrenyl (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鈥?0% 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.