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 m(2) 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 cm(2) 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 pi-electronic functions, in addition to their gas adsorption properties thus far reported.

A review: methane capture by nanoporous carbon materials for automobiles

“…Furthermore, conjugated microporous polymers (CMPs) have been of interest because of their porous structures with organic functionalities, for such applications as gas storage, capture, and separation [61][62][63][64]. In particular, the committee of CMPs offers novel materials capable of CH 4 storage and their properties can be reduced effectively.…”

In Situ Growth of Flexible Polyphenylene-Conjugated Microporous Polymer Films for Fluorescence Detection of the Total Quantity of Developing Agents and Their Oxidation Products

“…Compared with MOFs material [2,3], they could be almost immune to the thermal and humid environment owing to the rigid skeleton of CMPs and were probably applied for kinds of conditions. The features of the CMPs make it a good candidate for many applications including gas storage [4][5][6][7], heterogeneous catalysis [8,9], light emitters [10][11][12] and light harvesting [13,14].…”

Targeted synthesis of electroactive porous organic frameworks containing triphenyl phosphine moieties

“…Recently, ultra high surface area covalent-linked porous organic frameworks (POFs) such as porous aromatic framework (PAF) [1][2][3][4][5], conjugated microporous polymer [6][7][8][9][10], covalent triazine-based framework [11], polymers of intrinsic microporosity [12,13], hyper-cross-linked polymer [14,15] and covalent organic framework [16][17][18] formed by organic polymerization method have emerged as an important platform in host-guest chemistry. The properties of POFs are crucially affected by their porosity when applied as a sorbent.…”