From Bowls to Capsules: Assembly of Hexanuclear NiII Rings Tailored by Alkali Cations |
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| Authors: | Dr Júlia Mayans Dr Constantinos C Stoumpos Dr Mercé Font-Bardia Prof Albert Escuer |
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| Institution: | 1. Instituto de Ciencia Molecular (ICMol), Universidad de Valencia, Jose Beltran 2, 46980 Paterna (Valencia), Spain;2. Department of Materials Science and Technology, University of Crete, P. O. Box 2208, 71003 Heraklion, Greece;3. Departament de Mineralogia, Cristallografia i Dipòsits Minerals and Unitat de Difracció de R-X. Centre Científic i Tecnològic (CCiTUB), Universitat de Barcelona, Martí Franqués s/n, Barcelona, 08028 Spain;4. Departament de Química Inorgànica i Orgànica, Secció Inorgànica and Institut de Nanociència i Nanotecnologia (IN2UB), Universitat de Barcelona, Martí i Franques 1–11, Barcelona, 08028 Spain |
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| Abstract: | An anionic hexanuclear NiII metallamacrocycle with endo and exo linking sites has been employed as a building block to generate a series of capsules and bowls of nanometric size. The supramolecular arrangement of the {Ni6} rings was tailored by the size of the alkali cations, showing the transition from {Ni6-M2-Ni6} capsules (M=LiI and NaI) to {Ni6-M} bowls (M=KI and CsI). The alkyl co-cations are determinant to stabilize the assemblies by means of CH⋅⋅⋅π interactions on the exo side of the metallamacrocycles. The effect on the topology of the supramolecular assemblies of the cation size, cation charge, Et3NH+ or Me4N+ counter cations has been analyzed. Magnetic measurements reveal the presence of ferromagnetic and antiferromagnetic interactions inside the rings that allow a S=0 ground state. |
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| Keywords: | capsules magnetism metallamacrocycles nickel self-assembly |
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