Light-Harvesting Conjugated Microporous Polymers: Rapid and Highly Efficient Flow of Light Energy with a Porous Polyphenylene Framework as Antenna

Abstract

The molecular design of light-harvesting antennae requires not only the segregation of a large number of chromophore units in a confined nanospace but also the cooperation of these units in achieving highly efficient energy transduction. This article describes the synthesis and functions of a polyphenylene-based conjugated microporous polymer (PP-CMP). PP-CMP was recently designed and synthesized by Suzuki polycondensation reaction and used as an antenna for the noncovalent construction of a light-harvesting system. In contrast to linear polyphenylene, PP-CMP consists of conjugated three-dimensional polyphenylene scaffolds and holds inherent porous structure with uniform pore size (1.56 nm) and large surface area (1083 m² g⁻¹). It emits blue photoluminescence, is capable of excitation energy migration over the framework, and enables rapid transportation of charge carrier with intrinsic mobility as high as 0.04 cm² V⁻¹ s⁻¹. The microporous structure of PP-CMP allows for the spatial confinement of energy-accepting coumarin 6 molecules in the pores and makes the high-throughput synthesis of light-harvesting systems with designable donor−acceptor compositions possible. Excitation of the PP-CMP skeleton leads to brilliant green emission from coumarin 6, with an intensity 21-fold as high as that upon direct excitation of coumarin 6 itself, while the fluorescence from PP-CMP itself is wholly quenched as a result of energy transfer from the light-harvesting PP-CMP framework to coumarin 6. The PP-CMP skeleton is highly cooperative, with an average of 176 phenylene units working together to channel the excitation energy to one coumarin 6 molecule, and features the energy-transfer process with quick, efficient, and vectorial character. These unique characteristics clearly originate from the conjugated porous structure and demonstrate the usefulness of CMPs in the exploration of π-electronic functions, in addition to their gas adsorption properties thus far reported.