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超分子自组装 Functional Organometallic Complexes Ying-Feng Han* 1 College of Chemistry & Materials Science, Northwestern University, 710000, Xi’an China 2 Department of Chemistry, Fudan University, 200433 Shanghai, China E-mail: [email protected] Recently, based on the successful construction of organometallic molecular assemblies1,2 using polydentate ligands with N-heterocyclic carbene donor functions, we have recently been able to perform photochemical modification (PCM) reactions on rectangular metalacycles built from bridging dicarbene ligands and featuring internal olefin groups via a photochemical [2+2] cycloaddition reaction.3 These results indicate the suitability of the [M2(dicarbene)2]2+ (M = Ag, Au) metalacycles as scaffolds for the photodimerization of the olefinic bonds to yield cyclobutane units within the molecular rectangles. While complexes feature an internal cyclobutane unit obtained by [2+2] cycloaddition of internal olefinic bonds, we also became interested in utilizing [M2(dicarbene)2]2+ (M = Ag, Au) complexes with terminal double bonds, which upon [2+2] cycloaddition would lead to complexes featuring a macrocyclic ligand as in. Removal of the metal atoms from such assemblies leads to interesting new macrocycles. The desired molecular size of the tetraimidazolium macrocycle can be tuned easily by changing the length and breadth of the internal bridging groups of ligands. This system presents an excellent starting point for a new method to multipurpose receptors. We have found that H2 can initiate unusual transformations between organometallic assemblies.4 If the Cp* group acts as a monodentate ligand, then the reversible constitutional switching between the two distinct complexes is accompanied by reversible changes in the coordination mode of the metal center from triangular to tetrahedral coordination geometries. The present system reversibly provides a foundation on which to develop organometallic switching systems that can be triggered by hydrogen. References 1 a) Han, Y.-F.; Jia, W.-G.; Yu, W.-B.; Jin, G.-X. Chem. Soc. Rev. 2009, 38, 3419-3434; b) Han, Y.-F.; Jin, G.-X. Chem. Soc. Rev. 2014, 43, 2799-2823; c) Han, Y.-F.; Jin, G.-X. Acc. Chem. Res. 2014, 47, 3571-3579. 2 a) Han, Y.-F.; Jia, W.-G.; Lin, Y.-J.; Jin, G.-X. Angew. Chem., Int. Ed. 2009, 48, 6234-6238; b) Li, H.; Han, Y.-F.; Lin, Y.-J.; Guo, Z.-W.; Jin, G.-X. J. Am. Chem. Soc. 2014, 136, 2982-2985. 3 a) Han, Y.-F.; Jin, G.-X.; Hahn, F. E. J. Am. Chem. Soc. 2013, 135, 9263-9266; b) Han, Y.-F.; Jin, G.-X.; Daniliuc, C. G.; Hahn, F. E. Angew. Chem. Int. Ed. 2015, 54, 4958-4962. 4 Han, Y.-F.; Zhang, L.; Weng, L.-H.; Jin, G.-X. J. Am. Chem. Soc. 2014, 136, 14608−14615.