Guo Huang, Hanhui Xu, Xiao-Ping Zhou, Zhengtao Xu,* Kunhao Li, Matthias Zeller, and Allen D. Hunter

Abstract: This paper reports on the strong tendency of a group of thioether and selenoether molecules to adopt non-centrosymmetric and non-interpenetrating features in forming 3D coordination networks with metal ions. We illustrate such tendency with the (10, 3)-a nets formed by Ag(I) ions and the large aromatic ligands of 1,3,6,8-tetrakis(phenylseleno)pyrene (TPhSeP) and 2,3,6,7,10,11-hexakis(phenylseleno)triphenylene (HPhSeT). In particular, TPhSeP interacts with AgSbF6 to provide a 3D chiral network based on trimeric coordination building blocks. Each trimeric building block is rather complex and consists of three pairs of TPhSeP molecules integrated through the Ag+ ions into a circular unit. The circular, trimeric units function as the three-connected nodes, which are further connected through the Ag+ ions to generate the (10, 3)-a topology. By comparison, the connectivity of the HPhSeT-based net is simpler, with the trigonal-shaped HPhSeT molecules acting as three-connected nodes that are integrated into a (10, 3)-a topology by means of the bridging Ag(I) ions. Other related networks are also briefly discussed to further illustrate the potential generality of the occurrence of non-centrosymmetric and non-interpenetrating features in networks formed by these molecules.

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