Research group of Professor Xie Yongshu of East China University of science and technology: Research on synthesis, structure and performance precise regulation and application of new porphyrins and isoporphyrins

Lead porphyrin, known as "living pigment", widely exists in natural functional systems such as chlorophyll and heme, which has important physiological activity and outstanding photoelectric performance The development of new porphyrins with novel structures and unique properties, heteroporphyrins and their dimers with similar structures to porphyrins, so as to further expand their structures and properties, has important value and attracted widespread attention Recently, the research group of Xie Yongshu, Professor of East China University of science and technology, used thiophene to activate the ring opening and desulfurization reaction, realized the interesting large ring rearrangement reaction and unique parallel connection structure, and synthesized a new type of heteroporphyrin with special overall aromaticity and local aromaticity; and successfully constructed three different pyrrole site linked heteroporphyrins by using the unique large ring transformation reaction developed in the early stage of the research group- Porphyrin dimer Relevant research results have been published in J am Chem SOC (DOI: 10.1021 / JACS 8b13148), angel Chem Int ed (DOI: 10.1002 / anie 201900010) and chem SCI (chem SCI., 2019, 10, 2186) Brief introduction of Professor jieyongshu's research group the main research direction of Professor jieyongshu's research group is porphyrin chemistry Around porphyrin, an important functional molecule widely existing in nature, systematic research on the design, synthesis, functional regulation and application of New Porphyrin conjugated structure guided by special functions is carried out In recent years, the research group has made a series of important achievements and published a series of high-level papers (angel Chem Int ed., DOI: 10.1002/anie.201900010; j.am Chem SOC., DOI: 10.1021/jacs.8b13148; chem SCI 2019, 10, 2186; chem Rev 2017, 117, 2203; angel Chem Int ed 2016, 55, 3063; j.am Chem SOC 2015, 137, 14055; chem Soc Rev ., 2015 , 44 , 1101; Angew Chem Int Ed , 2014 , 53 , 10955; Angew Chem Int.Ed , 2014 , 53 , 14069; J Am Chem Soc ., 2013 , 135 , 19119 ）。 Prof Xie Yongshu received his Ph.D in 1998 from the Department of chemistry of Zhejiang University; he went to the Department of chemistry of University of science and technology of China to engage in postdoctoral research in the same year and remained as an associate professor in July 2000 From 2003 to 2007, he visited Taiwan University, Kyushu University and National Institute of materials In August 2007, he returned to China and was employed as a professor in the school of chemistry and molecular engineering of East China University of science and technology He has successively been selected as Shanghai Pujiang talents, excellent talents of the Ministry of education in the new century, special professor of Shanghai Oriental Scholars, and vice chairman of porphyrin and phthalocyanine Professional Committee of the Chinese chemical society So far, 186 SCI papers have been published, all of which have been cited 4500 times, including 3400 times in the past five years, and the high cited h index is 41 It was featured twice by angelw Chem Int ed highlight Obtained 2 US invention patents At present, 6 papers have been selected as "highly cited papers" of ESI, and 3 papers have been selected as "hot papers" of ESI Frontier research achievements: first, through thiophene activation, ring opening and desulfurization, the realization of unique large ring rearrangement and parallel connection reaction, the research of large ring transformation reaction of isophyrphyrin is helpful to develop new isophyrphyrin framework, further expand structure and performance, and has important value Based on a series of previous studies, a new strategy to control the structure and aromaticity of heteroporphyrin macrocycles has been developed By introducing Thiophene Units into the porphyrin system, the novel heteroporphyrins with special global and local aromaticity were successfully synthesized by using dislocation pyrrole units to activate thiophene's ring opening and desulfurization reaction, realizing interesting large ring rearrangement reaction and unique parallel connection structure Based on this method, we can further design and synthesize a new type of heteroporphyrin with unique structure and performance, expand its structure and function, and apply it to new organic photoelectric functional materials and other fields Relevant research results were published in angelw Chem Int ed (DOI: 10.1002/anie.201900010) Fig 1 Synthesis route of new type of heteroporphyrin with special global and local aromaticity (source: angelw Chem Int ed.) 2 High regioselectivity construction of new type of heteroporphyrin porphyrin dimer and energy transfer regulation of two porphyrin phase units generated by covalent linkage, energy in the molecule/ Electron transfer, two-photon absorption and nonlinear optics have unique properties However, there is still a lack of effective strategies to construct dimers of porphyrins, especially the heteroporphyrin porphyrin dimers In this work, three novel pentaporphyrin intermediates with high regioselectivity were successfully synthesized by combining the macrocycle transformation strategy developed in the early stage with the high efficient halogenation reaction Furthermore, the heteroporphyrin porphyrin dimers linked with three different pyrrole sites were successfully constructed by the Sonogashira reaction coupled with zinc porphyrin alkyne The results show that there is a controllable energy transfer process from porphyrin to heteroporphyrin in dimer Interestingly, compared with α - linked dimers, β - linked dimers have higher intramolecular energy transfer efficiency Based on this strategy, heteroporphyrin dimers or polymers with unique structures and properties can be further designed and synthesized, which can be used in the fields of organic photoelectric functional materials Relevant research results were published in J am Chem SOC (DOI: 10.1021 / JACS 8b13148) Fig 2 Construction of three different pyrrole linked heteroporphyrin porphyrin dimers (source: J am Chem SOC.) 3 Construction of a new type of "bundled" porphyrin to prepare high-efficiency dye-sensitized solar cells In response to the energy crisis and environmental pollution caused by fossil fuels, various types of solar cells have attracted extensive attention Among them, dye-sensitized solar cells have the advantages of simple preparation, low cost and high photoelectric conversion efficiency Porphyrin dye is an important sensitizer for solar cells In view of the serious aggregation of porphyrin macrocycles and other problems, on the basis of previous research, the researchers changed the traditional long carbon chain wrapped porphyrin into the "bundle" type carbon chain wrapped porphyrin, and synthesized new porphyrin dyes xw40 and xw41, so as to more effectively inhibit dye aggregation and electronic recombination, extend electronic life, improve charge collection efficiency, current and voltage The researchers further used a combination of CO sensitization and CO adsorption strategy to improve the photoelectric conversion efficiency; further through the inclusion of electronic donors, the introduction of polyethylene glycol chain in the donor unit and other strategies, the photoelectric conversion efficiency can be increased to 12.1% This series of research provides a new idea for the design and synthesis of high efficiency porphyrin dyes, and also enriches and develops porphyrin synthesis chemistry Relevant research results were published in Chem SCI (chem SCI 2019, 10, 2186); ACS Applied Materials & interfaces (ACS Applied Materials & interfaces, 2019, 11, 5046) and chemsuschem (DOI: 10.1002/csc.201900139) Figure 3 Structure of the new "bundled" porphyrin (source: chem SCI) The above research was mainly completed by doctoral students li Qizhao, Zeng Kaiwen and Lu Yunyue under the guidance of Professor Xie Yongshu and Associate Professor Li Chengjie In terms of mechanism research and spectral test, Professor Hiroyuki Furuta of Kyushu University in Japan and Yanshi University in South Korea were obtained Great help from Professor Dongho Kim In addition, Professor Zhu Weihua's research group of Jiangsu University, Professor Hans ޹ gren's research group of Sweden's Royal Institute of technology and Professor Zhang Zaichao of Huaiyin Normal University have provided a lot of help in electrochemical test, theoretical calculation and crystal structure test At the same time, it has been carefully guided by academician Tian He and supported by NSFC, Shanghai Science and technology major project, Shanghai Science and technology international cooperation and Shanghai University Distinguished Professor (Oriental scholar) and other projects Nowadays, people and scientific research have been paid more and more attention in the economic life China has ushered in the "node of science and technology explosion" Behind the progress of science and technology is the work of countless scientists In the field of chemistry, in the context of the pursuit of innovation driven, international cooperation has been strengthened, the influence of Returned Scholars in the field of R & D has become increasingly prominent, and many excellent research groups have emerged in China For this reason, CBG information adopts the 1 + X reporting mechanism CBG information, chembeangoapp, chembeango official microblog, CBG wechat subscription number and other platforms jointly launch the column of "people and scientific research", approach the domestic representative research group, pay attention to their research, listen to their stories, record their demeanor, and explore their scientific research spirit.