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Author (up) Liu, H.; Luo, J.C.; Shan, W.P.; Guo, D.; Wang, J.; Hsu, C.H.; Huang, M.J.; Zhang, W.; Lotz, B.; Zhang, W.B.; Liu, T.B.; Yue, K.; Cheng, S.Z.D. openurl 
  Title Manipulation of Self-Assembled Nanostructure Dimensions in Molecular Janus Particles Type Journal Article
  Year 2016 Publication ACS Nano Abbreviated Journal ACS Nano  
  Volume 10 Issue 7 Pages 6585-6596  
  Keywords Janus particles; self-assembly; nanobelts; nanosheets; polyoxometalates  
  Abstract The ability to manipulate self-assembly of molecular building blocks is the key to achieving precise “bottom-up” fabrications of desired nanostructures. Herein, we report a rational design, facile synthesis, and self assembly of a series of molecular Janus particles (MJPs) constructed by chemically linking alpha-Keggin-type polyoxometalate (POM) nanoclusters with functionalized polyhedral oligomeric silsesquioxane (POSS) cages. Diverse nanostructures were obtained by tuning secondary interactions among the building blocks and solvents via three factors: solvent polarity, surface functionality of POSS derivatives, and molecular topology. Self-assembled morphologies of KPOM-BPOSS (B denotes isobutyl groups) were found dependent on solvent polarity. In acetonitrile/water mixtures with a high dielectric constant, colloidal nanoparticles with nanophase-separated internal lamellar structures quickly formed, which gradually turned into one-dimensional nanobelt crystals upon aging, while stacked crystalline lamellae were dominantly observed in less polar methanol/chloroform solutions. When the crystallizable BPOSS was replaced with noncrystallizable cyclohexyl-functionalized CPOSS, the resulting KPOM-CPOSS also formed colloidal spheres; however, it failed to further evolve into crystalline nanobelt structures. In less polar solvents, KPOM-CPOSS crystallized into isolated two-dimensional nanosheets, which were composed of two inner crystalline layers of Keggin POM covered by two monolayers of amorphous CPOSS. In contrast, self-assembly of KPOM-2BPOSS was dominated by crystallization of the BPOSS cages, which was hardly sensitive to solvent polarity. The BPOSS cages formed the crystalline inner bilayer, sandwiched by two outer layers of Keggin POM clusters. These results illustrate a rational strategy to purposely fabricate self-assembled nanostructures with diverse dimensionality from MJPs with controlled molecular composition and topology.  
  Address [Liu, Hao; Luo, Jiancheng; Shan, Wenpeng; Guo, Dong; Wang, Jing; Hsu, Chih-Hao; Huang, Mingjun; Zhang, Wei; Liu, Tianbo; Yue, Kan; Cheng, Stephen Z. D.] Univ Akron, Coll Polymer Sci & Polymer Engn, Dept Polymer Sci, Akron, OH 44325 USA, Email: tliu@uakron.edu;  
  Corporate Author Thesis  
  Publisher Amer Chemical Soc Place of Publication Editor  
  Language English Summary Language Original Title  
  Series Editor Series Title Abbreviated Series Title  
  Series Volume Series Issue Edition  
  ISSN 1936-0851 ISBN Medium  
  Area Expedition Conference  
  Notes WOS:000380576600021 Approved no  
  Call Number Admin @ benzerara @ Serial 14033  
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