title: A Filled-Honeycomb-Structured Crystal Formed by Self-Assembly of a Janus Polyoxometalate-Silsesquioxane (POM-POSS) Co-Cluster.
abstract: Clusters with diverse structures and functions have been used to create novel cluster-assembled materials (CAMs). Understanding their self-assembly process is a prerequisite to optimize their structure and function. Herein, two kinds of unlike organo-functionalized inorganic clusters are covalently linked by a short organic tether to form a dumbbell-shaped Janus co-cluster. In a mixed solvent of acetonitrile and water, it self-assembles into a crystal with a honeycomb superstructure constructed by hexagonal close-packed cylinders of the smaller cluster and an orderly arranged framework of the larger cluster. Reconstruction of these structural features via coarse-grained molecular simulations demonstrates that the cluster crystallization and the nanoscale phase separation between the two incompatible clusters synergistically result in the unique nano-architecture. Overall, this work opens up new opportunities for generating novel CAMs for advanced future applications.
authors.affiliation: Center for Synthetic Soft Materials, Key Laboratory of Functional Polymer Materials of Ministry of Education and Institute of Polymer Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin, 300071 (P. R. China).
authors.forename: Chi
authors.initials: C
authors.lastname: Ma
authors.affiliation: Center for Synthetic Soft Materials, Key Laboratory of Functional Polymer Materials of Ministry of Education and Institute of Polymer Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin, 300071 (P. R. China).
authors.forename: Han
authors.initials: H
authors.lastname: Wu
authors.affiliation: Department of Chemical Engineering, Tsinghua University, Beijing, 100084 (P. R. China).
authors.forename: Zi-Han
authors.initials: ZH
authors.lastname: Huang
authors.affiliation: Department of Chemical Engineering, Tsinghua University, Beijing, 100084 (P. R. China).
authors.forename: Ruo-Hai
authors.initials: RH
authors.lastname: Guo
authors.affiliation: Center for Synthetic Soft Materials, Key Laboratory of Functional Polymer Materials of Ministry of Education and Institute of Polymer Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin, 300071 (P. R. China).
authors.forename: Min-Biao
authors.initials: MB
authors.lastname: Hu
authors.affiliation: Karlsruhe Nano Micro Facility and Institute of Nanotechnology, Hermann-von-Helmholtz-Platz 1, 76344, Eggenstein-Leopoldshafen (Germany). christian.kuebel@kit.edu.
authors.forename: Christian
authors.initials: C
authors.lastname: Kübel
authors.affiliation: Department of Chemical Engineering, Tsinghua University, Beijing, 100084 (P. R. China). ltyan@mail.tsinghua.edu.cn.
authors.forename: Li-Tang
authors.initials: LT
authors.lastname: Yan
authors.affiliation: Center for Synthetic Soft Materials, Key Laboratory of Functional Polymer Materials of Ministry of Education and Institute of Polymer Chemistry, Collaborative Innovation Center of Chemical Science and Engineering (Tianjin), Nankai University, Tianjin, 300071 (P. R. China). weiwang@nankai.edu.cn.
authors.forename: Wei
authors.initials: W
authors.lastname: Wang
keywords: Janus co-cluster; nanomaterials; polyoxometalates; self-assembly; silsesquioxanes