Synthesis Of BODIPY Based Conjugated Microporous Polymer And Their Application In Photocatalysis

Inspired by nature,development of efficient photosensitizers(PSs)for artificial photosynthesis is of great importance to alleviate energy crisis and environmental pollution by efficiently harvesting solar energy.For the past few years,many photocatalysts are mainly composed of metal complexes and finely synthesized organic molecules have been continually reported for photocatalytic organic transformations using visible light.These homogeneous PSs were limited by noble metal,toxic elements,and the difficulty in recycling,severely hindering their practical application.To improve the utilization of solar light,the development of efficient and sustainable PSs is necessary.Conjugated microporous polymers(CMPs),with high surface area and structural designability,offer a great platform for constructing highly efficient heterogeneous PSs.However,it is still lacking rational and general strategy for developing heavy atom free(HAF)CMP PSs with highly efficient sensitizing ability.Herein,we explore a HAF photosensitization protocol by filling polycyclic aromatic hydrocarbons into the mother CMP(CMP-1),resulting in a series of CMPs(CMP-2—4)with much enhanced photosensitization ability.Systematic study reveals that covalent modification of CMP with polycyclic aromatic hydrocarbons can promote intra-framework charge transfer to facilitate both intersystem crossing(ISC)and electron-hole separation for efficient interface energy and electron transfer to boost both energy-and electron-transfer reactions.Especially,the yield of methyl phenyl sulfoxide can reach to as high as 92% for CMP-2,significantly higher than that of CMP-1(32%).Experiments and theory calculations demonstrated the structure-property-activity relationship of these CMPs,opening a new avenue for developing HAF heterogeneous PSs with highly efficient sensitizing activity by rational regulation at the molecular level.This work not only establishes an efficient strategy to improve photosensitization in CMPs,but also opens up a new protocol for the design of heterogeneous heavy atom free PSs with efficient interface energy transfer and electron transfer.