Project team of Professor Yin Shouchun of Hangzhou Normal University: Construction of metal macrocyclic / cage based fluorescent supramolecular polymer and regulation of its luminescent properties

Introduction in recent years, fluorescent supramolecular polymer is a hot topic in the field of functional supramolecular polymer research, which benefits from the introduction of fluorescent groups can greatly expand the application of supramolecular polymer There are many fluorescent groups in the fluorescent supramolecular polymer, so when designing this kind of dynamic polymer, the fluorescent groups with specific properties can be introduced into the molecule according to the practical application needs When the group with aggregation induced luminescence (AIE) effect is introduced into the supramolecular polymer, the resulting supramolecular polymer has good luminescent properties in both high concentration solution and solid state Therefore, the research of fluorescent supramolecular polymer provides a new idea for the development of new photoelectric materials and fluorescent probes Recently, the research group of Professor Yin Shouchun, School of materials and chemical engineering, Hangzhou Normal University, has made the latest progress in the field of fluorescent supramolecular polymers, and the relevant results have been published in J am Chem SOC (DOI: 10.1021 / JACS 8b10842) Professor Yin Shouchun profile professor Yin Shouchun, graduated from the Department of polymer science and engineering, University of Science & Technology China in 2005 From 2006 to 2007, he worked as a postdoctoral researcher in the Department of chemistry, Tsinghua University, under the guidance of academician Zhang Xi From 2008 to 2010, he worked as a postdoctoral researcher in the Department of chemistry, University of Leuven, Belgium, under the guidance of Professor win dehaen He joined Hangzhou Normal University in July 2010 From 2015 to 2016, he worked as a visiting scholar in the Department of chemistry of the University of Utah in the United States and studied with Academician Peter stang He is mainly engaged in the research of supramolecular polymer, photoelectric functional polymer materials and fluorescent probes He has successively presided over 4 National Natural Science Foundation projects (1 major research program cultivation project, 2 general projects, 1 youth project), 2 Zhejiang Natural Science Foundation projects and 1 first class funded project of China Postdoctoral Science Foundation project, and authorized 7 invention patents More than 80 academic papers have been published in proc Natl Acad SCI., j.am Chem SOC., angel Chem Int ed., chem Commun., chem EUR J., polymer Chem And other domestic and foreign journals He has successively been selected as the academic leader of young and middle-aged people in Zhejiang Province, the first level of "131" talents in the new century in Hangzhou city; he has won the honors of excellent teachers in Zhejiang Province, ten thousand Excellent Communist Party members in Zhejiang Province, advanced individuals in Zhejiang Province with "consideration of career and family", and advanced individuals in the third session of teachers' Ethics in Hangzhou city Research achievements: in recent years, with the support of NSFC and Zhejiang Natural Science Foundation, Professor Yin Shouchun's research group has made important progress in the field of fluorescent supramolecular polymerization Firstly, triphenylamine group, tetrastyrene group and pyrene group were introduced to the bipyridyl group containing ligands respectively, and three kinds of organometallic supramolecular assemblies with different fluorescence emission were constructed by self-assembly driven by metal coordination with organoplatinum receptor containing 24-crown-7 group After the second-order ammonium salt guest molecules with blue fluorescence are added to the assemblies, supramolecular polymers with blue, green and yellow fluorescence are formed through host guest interaction self-assembly, and the fluorescence color of these supramolecular polymers can change with the concentration of the system The researchers further constructed a supramolecular polymer (Fig 1) emitting white fluorescence by using complementary luminescence properties (aggregation fluorescence quenching and aggregation induced luminescence), complementary action of light (yellow light and blue light) and complementary host guest interaction (crown ether and secondary ammonium salt), which provided a new idea for the preparation of new luminescent materials (proc Natl Acad SCI 2017, 114, 3044 ）。
Figure 1 Synthesis of white fluorescent supramolecular polymer (source: proc Natl Acad SCI 2017, 114, 3044) Secondly, the researchers constructed a series of Pt (II) fluorescent supermolecular cages (Fig 2) that can regulate the luminescence by using metal coordination self-assembly, and realized the regulation of the luminescent properties of the assembly by changing the solvent, initially explored the application of the supermolecular cages in the detection of sulfhydryl amino acids (j.am.chem.soc 2017, 139, 5067 ）。
Figure 2 Pt (II) fluorescent supramolecular cage with controllable luminescence (source: J am Chem SOC 2017, 139, 5067) then, the researchers will have the AIE effect of the tetrastyryl tetrabenzoate ligand, the pyridine ligand with 24-crown-7 structure and the metal platinum receptor with two free coordination bonds, in acetone through the coordination of pyridine platinum and carboxylic acid platinum to form a structured metal cage with four host guest interactions with the secondary ammonium salt After that, the researchers constructed a fluorescent Supramolecular Gel based on the interaction between host guest and self-assembly of metal cage compounds (Figure 3) The supramolecular gel has the characteristics of stimuli responsive and self repairing, and has the characteristics of fluorescence and rigidity (J Am Chem Soc 2018, 140, 7674) Fig 3 fluorescent supramolecular gels based on metal cage compounds (source: J Am Chem Soc 2018, 140) 7674) further, the researchers synthesized a series of crown ether modified metal macrocycles (the yield is higher than 90%) by using the coordination driven self-assembly method By changing the functional groups of pyridine ligands in the macrocycles, the fluorescence of the metal macrocycles was regulated from blue light to red light Using the host guest interaction of crown ether and second-order ammonium salt, a series of fluorescence controlled supramolecular polymers were prepared (Fig 4) Due to the formation of supramolecular polymers, the arrangement of metal rings becomes more orderly, which reduces the accumulation of molecules and the effect of self quenching Compared with the metal macrocycles, the luminescent efficiency of the solution and the solid-state supramolecular polymers has been significantly improved Therefore, the yellow light super molecular polymer with high luminous efficiency was coated on the blue light LED materials, and a kind of LED material with white light emission was successfully prepared, which widened the luminous area of optical devices The results were published in J am Chem SOC (DOI: 10.1021 / JACS 8b10842) Figure 4 Structure of fluorescence controlled supramolecular polymer (source: J am Chem SOC Doi: 10.1021 / JACS 8b10842) about people and scientific research Today, science and technology elements are increasingly valued in 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.