Synthesis And Properties Research On Functional Porphyrin Compound

For its special photophysical and photochemical properties,porphyrin has been applied into many frontier fields,especially in photodynamic therapy and organic solar cells.The thesis focuses on synthesis and properties research of two-photon photosensitizers and organic solar cell materials based on porphyrin.The main contents are as follows:1.Porphyrin is one of main photosensitizers which have been approved for the clinic experiments.However,the application of porphyrin in photodynamic therapy has been limited for weak red and near-infrared absorption.Generally,the main absorption scope of porphyrin photosensitizer is about 400-500 nm.With two-photon technology,it can be extended to 800-1000 nm which is optimal scope for the treatment of deep seated tumors and large-size tumors.Therefore,the key to two-photon photodynamic therapy is to develop new porphyrin photosensitizers with stronger two-photon absorption,higher singlet oxygen quantum,better biocompatibility and higher targeting ability.The thesis has developed a novel lysosome-specific PDT agent,AlaPZn-PhenRu,an amphiphilic conjugate in which a porphyrin moiety and a polypyridyl Ru(II)moiety are covalently linked together via an ethynyl bridge.And alanine has been introduced into porphyrin moiety to improve its biocompatibility and water-solubility,which can also help photosensitizers to get into cancer cells selectively.According to related photophysical and photochemical experiments,maximum absorption of AlaPZn-PhenRu is 455 nm which has shifted obviously from maximum absorption of general porphyrins.And the compound has showed strong ability to generate singlet oxygen with high singlet oxygen quamtum(0.94)in air-saturated DMSO.The cell test in vitro has showed that the compound(730 nM)has little dark toxicity,but achieved a low IC50(310 nM)with 8 J/cm2 optical source.In all,it is a selectively cell permeable photosensitizer for two-photon photodynamic therapy.2.Porphyrin has good photoelectric properties for its large conjugate ring structure,especially strong absorbing ability in visible light and near infrared region,which makes it an important organic photoelectronic material in BHJ solar cell.However,most research of good small molecule material based on porphyrin in BHJ solar cell focused on Acceptor-Donor-Acceptor structure.This structure can be got with poisonous organotin and lithium reagent,and its planarity is not good which may affect electron transfer.In the thesis,two A-π-D-π-A donor materials(14BPZnRDN,NBPZnRDN),in which porphyrin moiety with different peripheral substituents has been covalently linked with rhodanine via an ethynyl bridge,and two A-π-D-π-A acceptor materials(TPPPZn,DiPPPZn),in which porphyrin moiety has been connected to perylene diimide via phenyl group,have been synthesized.Introducing of ethynyl makes molecule structure a conjugate plane structure and stronger conjugation effects to improve electron transfer.And synthesis process has adopted Sonogashira reaction without dangerous reagent.Related photophysical and photochemical research has showed that absorption edge of 14 BPZnRDN has been extended to 800 nm with Eg(1.67 eV)which makes it a narrow band gap donor material for more light-harvesting.And its photoelectric conversion efficiency has been 2.26 %,which is better than NBPZnRDN.Because introducing alkychain to beta position may improve self-assemble and filming property by changing its solubility and structure.The absorption scope of acceptor material TPPPZn is 450-530 nm,and the absorption scope of commercial donor material PCE-10 is 625-700 nm.The absorption scope of their mixed film,which is 350-800 nm,has showed strong conjugation effects and broadened peaks for their good matching.And its LUMO(-3.6 eV)makes it easier to acceptor electron and is close to fullerene material,which is an excellent acceptor material.The PCE of its device is 6.28 % with a high Jsc(12.51 mA·cm-2)and a high EQE(70 %),which is better than the device of DiPPPZn.Because introducing of perylene diimide may change its spatial structure arrangement and three-dimensional symmetrical configurations may be better for its self-assembling and photovoltaic property.Acceptor material TPPPZn has got a high PCE with a novel structure which may make it a future material in solar cell.There is no similar report on these two materials.