Preparation And Properties Of Subpthalocyanine-based Conjugated Microporous Polymer

Conjugated microporous polymers,as an emerging organic porous material,that offer a high flexibility in molecular design due to their unique?-conjugated skeletons with permanent nanopores,have been widely used in many fields.Subphthalocyanines?SubPc?are conjugated macrocycles with 14?-electron aromatic skeleton consisting of three isoindole units.It adopted a non-centrosymmetric near-plane conical structure.Due to their aromaticity,excellent thermal stability and chemical stability,the SubPc have rencently attracted much attention as a new function material.However,the reports of porous polymers containing subphthalocyanines are rare.In this paper,two kinds of conjugated microporous polymers based on phthalocyanine were designed and synthesized.Their structures and porous properties were characterized,in addition,we preliminarily explored their applications as porous materials.The main research contents are summarized as follows:1.SubPc-ThP1 and SubPc-ThP2 were synthesized by Pd-catalyzed Stille coupling reaction with 2,5-bis?trimethyltin?thiophene and 5,5-bis(trimethyltin-2,2'-bithiophene,respectively,using polybrominated Subphthalocyanines monomers as construction units.The Brunauer-Emmett-Teller?BET?surface area is 179 m2g^-1 and 152 m2g^-1,respectively,and the pore size are concentrated at 2.4 nm and 2.6 nm.Due to the influence of many factors,such as porosity and light capture ability,they also exhibit different iodine uptake capacities and photosensitizing abilities.Compared with SubPc-ThP2,SubPc-ThP1 exhibits considerable capture capacity for iodine in gaseous iodine and organic solvents.At 353 K,the adsorption capacity of iodine vapor was 203 wt%,and in iodine/cyclohexane solution,the capacity of iodine adsorbed was 139.8 mg/g,the removal rate of iodine reached 41.0%.In addition,SubPc-ThP1 as a photosensitizer,the absorption peak of singlet oxygen trapper was quenched about 90%at 690 nm illumination after 30 minutes.2.Two kinds of axially substituted SubPc-based conjugated porous polymers,SubPc-P1 and SubPc-P2,have been designed and synthesized by Pd-catalyzed Sonogashira cross-coupling reaction of Trihalogenated and Tetrahalogenated Subphthalocyanines with1,4-diethynylbenzene,respectively.The BET surface areas are evaluated to be 434 m2/g and106 m2/g for SubPc-P1 and SubPc-P2,respectively,and the pore diameters are mainly 2.8nm and 3.4 nm.Combining the porosity with N-rich feature and visible light harvesting capability,SubPc-P1 and SubPc-P2 can be used as iodine sorbents and photosensitizers for singlet oxygen generation.SubPc-P2 could absorb the iodine molecules more efficiently relative to SubPc-P1?280 wt%?.At 353 K,iodine vapor uptake capacities reaches 306.6wt%.In cyclohexane solution,the capacity of iodine adsorbed was 440.9 mg/g,and the removal rate was as high as 97.7%.In addition,SubPc-P1 as a photosensitizer can produce singlet oxygen more efficiently.The absorption peaks of about 90%of the singlet oxygen trapping agent can be quenched completely after 5 minutes of 690 nm illumination.