Selective Formation ofS₄- andT-Symmetric Supramolecular TetrahedralCages and Helicates in Polar Media Assembled via Cooperative Action of Coordination and HydrogenBonds

Qixun Shi*^a,f, Xiaohong Zhou^a, Wei Yuan^a, Xiaoshi Su^a, Algirdas Neniškis^b,Xin Wei^a, Lukas Taujenis^c, Gustautas Snarskis^b, Jas S. Ward^d, Kari Rissanen^d, Javier de Mendoza^eand Edvinas Orentas^b

^aInstitute of Advanced Synthesis, School of Chemistry and Molecular Engineering, Jiangsu National Synergetic Innovation Center for Advanced Materials, Nanjing Tech University, Nanjing 211816, China

^bDepartment of Organic Chemistry, Vilnius University, Naugarduko 24, LT-03225 Vilnius, Lithuania

^cThermo Fisher Scientific Baltics, V. A. Graičiūno 8, LT-02241, Vilnius, Lithuania

^dUniversity of Jyvaskyla, Department of Chemistry, P.O. Box 35, 40014 Jyväskylä, Finland

^eInstitute of Chemical Research of Catalonia (ICIQ), AV. Països Catalans, 16, 43007 Tarragona, Spain

^fState Key Laboratory of Fine Chemicals, Dalian University of Technology, Dalian 116024, China

Abstract:We report on the synthesis and self-assembly study of novel supramolecular monomers encompassing quadruple hydrogen-bonding motifs and metal-coordinating 2,2’-bipyridine units. When mixed with metal ions such as Fe²⁺or Zn²⁺, the tetrahedron cage complexes are formed in quantitative yields and full diastereoselectivity, even in highly polar acetonitrile or methanol solvents. The symmetry of the complexes obtained has been shown to depend critically on the flexibility of the ligand. Restriction of the rotation of the hydrogen-bonding unit with respect to the metal-coordinating site results in aT-symmetric cage, whereas introducing flexibility either through a methylene linker or rotating benzene ring allows the formation ofS₄-symmetric cages with self-filled interior. In addition, the possibility to select between tetrahedral cages or helicates and to control the dimensions of the aggregate has been demonstrated withathree-component assembly using external hydrogen-bonding molecular inserts or by varying the radius of the metal ion (Hg²⁺vsFe²⁺). Self-sorting studies of individual Fe²⁺complexes with ligands of different sizes revealed their inertness toward ligand scrambling.

J. Am. Chem. Soc.2020,142,3658–3670(2020年影响因子:14.695).

论文连接：https://pubs.acs.org/doi/abs/10.1021/jacs.0c00722