Li Dan, Jinan University / Zhou Xiaoping, Shantou University research team: self-assembly of chiral organopentahedral

Introduction: self-assembly is the essential characteristic of supramolecular chemistry and biological system Chemists have designed and synthesized many organometallic cages with exquisite structures by using coordination directed self-assembly method These cages have interesting functions, such as separation, recognition, catalysis, stabilization of active species, drug loading and so on Although this field has made great progress, it is very difficult to use a large number of components for one-step self-assembly to obtain organometallic cages with complex structures, and it is a great challenge to obtain cages with single chirality Recently, Professor Li Dan of Jinan University and Professor Zhou Xiaoping of Shantou University have made new breakthroughs in the field of self-assembled supramolecular chemistry Professor Li Dan, Professor Li Dan (source: School of chemistry and materials, Jinan University), professor and doctoral supervisor of Jinan University He was the vice president of Shantou University and the dean of the school of chemistry and materials of Jinan University in 2016 He received his bachelor's degree in chemistry from Sun Yat sen University in 1984 and his doctor's degree from Hong Kong University in 1993 Professor Li Dan is the winner of National Science Fund for Distinguished Young Scholars His main research interests are the synthesis, crystal structure and function of supramolecular assembly, assembly, morphology and functionalization of nano materials Professor Li Dan is a "government special allowance expert" of the State Council He was selected into the leading talent plan (ten thousand talents plan) of "one million talents project in the new century" He has won the first prize of science and technology of Guangdong Province (the first adult) and "model worker" of Guangdong Province He is now a member of the Royal Society of Chemistry (FRSC), director of the Chinese Chemical Society and vice president of Guangdong chemical society Presided over the key supporting projects of NSFC major research plan, national 973 Plan (Project Leader), NSFC general projects, etc The related research work was published by the first author or corresponding author in J am Chem SOC., angelw Chem Int ed and other international authoritative chemical academic journals, with H-index of 48 and SCI papers cited by him more than 5000 times Professor Zhou Xiaoping (source: School of science, Shantou University), Professor Zhou Xiaoping, Shantou University He received his bachelor's degree from Wuhan University of science and technology in 2003, his master's degree from Shantou University in 2006 and his doctor's degree from City University of Hong Kong in 2010 Professor Zhou Xiaoping's research interests mainly focus on crystal engineering, metal organic porous materials and photoelectric functional complex materials Professor Zhou Xiaoping has won the first prize of science and technology of Guangdong Province, presided over the National Natural Science Foundation, Guangdong Natural Science Foundation, Guangdong Natural Science outstanding youth fund, etc He has published more than 40 scientific research papers in top chemical academic journals such as J am Chem SOC.; angelw Chem Int ed.; chem Commun Self-assembly of chiral organometallic pentagonal tetrahedron Recently, Professor Li Dan of Jinan University / Professor Zhou Xiaoping of Shantou University used solvothermal sub component self-assembly technology to assemble 2-methyl-4-imidazolaldehyde, m-phenylenedimethylamine, cobalt salt and other non chiral building elements in one step to obtain a 72 component metal organic cage (top left of the figure below) The cage like complex has a very rare pentagonal tetrahedral structure, with The enantiomeric mixture can be formed by the spontaneous resolution of crystallization, and the single chiral product can be obtained by the resolution of inducer The results of X-ray single crystal diffraction of metal organic cage (source: j.am Chem SOC.) containing 72 components show that the cage compound is a polyhedron with 20 metal vertices, which is determined as pentagonal tetrahedron according to the following structural features: 1) the structure contains 12 irregular pentagons and the molecule itself has t Symmetry; 2) there are three different coordination environment metals as the vertex (4 + 4 + 12); 3) there are three different length ligands as the edge (6 + 12 + 12); 4) the structure itself is chiral Interestingly, the pyroxene in nature also has the structural characteristics of pentagonal tetrahedron It is understood that the cage complex is the first reported synthetic molecule with pentagonal tetrahedral structure, and contains 72 components, which is the most cage complex components obtained by self-assembly of secondary components Under the guidance of a single chiral menthol with multiple chiral centers and hydroxyl groups, the enantiomeric cages with excessive enantiomers can be obtained Through a series of synthesis experiments, the author speculated that the reasons for the formation of organometallic pentahedral tetrahedron were as follows: 1) replace the 2-and 5-position substituent groups on imidazolaldehyde, when the 2-position substituent is methyl, the crystal product obtained is organometallic pentahedral tetrahedral cage, while when the 2-position is hydrogen atom, the crystal product obtained is cubic cage, and the 5-position substituent has no effect on the shape of cage It may be that when the 2-position has a large substituent, due to the influence of steric hindrance, the cage window is propped up and assembled into a pentagonal window; 2) the anions involved in the reaction are replaced with ClO 4 +, Pf 6 ￣, CF 3So 3 ￣ instead of BF 4 ￣ can be successfully assembled to obtain similar crystalline cage like complexes, but when no 3 ￣, Cl ￣, Br ￣ and other anions are introduced, crystalline products cannot be obtained, which indicates that the influence of anions cannot be ignored in the process of assembling the metal organic cage Because cage complexes and anions can form a three-dimensional framework with diamond (DIA) topological structure through nonclassical hydrogen bonding, the author has proved that the supramolecular framework has permanent holes through the gas adsorption experiments of N2 and CO2 Compared with similar materials, it has a medium strength adsorption capacity for CO2 Previously, the team has accumulated rich experience in the research of secondary component self-assembly synthesis of organometallic cages and their chirality, adsorption and reaction (JACS 2012, 8042; 2013, 16062; angel.chem Int ed 2015, 6190) This achievement is the latest progress in a series of research Relevant information of Professor Zhou Xiaoping: http://sci.stu.edu.cn/mainsite/person.aspx?person_id=47