NDLI: One pot-synthesis of chiral Ni $_{6}$ clusters involving Ni $_{3}$ subunits: a combined structural, magnetic and DFT study

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Sanmartín, Jesús Ocampo, Noelia Fondo, Matilde Cano, Joan García-deibe, Ana M.
Description	Author Affiliation: Fondo M ( Departamento de Química Inorgánica, Facultade de Ciencias, Universidade de Santiago de Compostela, 27002, Lugo, Spain. matilde.fondo@usc.es)
Abstract	Ni $_{6}$ clusters of the general formula $[\{Ni_{3}L^{n}(OAc)(OH)\}_{2}(X)(OAc)(H_{2}O)_{2}]$ (n = 1, 2; X = Cl $^{−}$ or $N_{3}^{−},$ (L $^{n})$ $^{3}$ $^{−}$ = hexadentate tritopic ligands) can be isolated by spontaneous self-assembly , from mixtures of Ni(OAc) $_{2}$ , $H_{3}L^{n},$ $NMe_{4}OH·5H_{2}O$ and NaX in adequate molar ratios. Thus, four new hexanuclear complexes $[\{Ni_{3}L^{1}(OAc)(OH)\}_{2}Cl(OAc)(H_{2}O)_{2}]·7.5H_{2}O$ $(1·7.5H_{2}O),$ $[\{Ni_{3}L^{2}(OAc)(OH)\}_{2}Cl(OAc)(H_{2}O)_{2}]·2H_{2}O·7.5MeOH$ $(2·2H_{2}O·7.5MeOH),$ $[\{Ni_{3}L^{1}(OAc)(OH)\}_{2}(N_{3})(OAc)(H_{2}O)_{2}]·6H_{2}O$ $(3·6H_{2}O)$ and $[\{Ni_{3}L^{2}(OAc)(OH)\}_{2}(N_{3})(OAc)(H_{2}O)_{2}]·4H_{2}O$ $(4·4H_{2}O)$ were obtained and fully characterised. $1·7.5H_{2}O$ and $2·2H_{2}O·7.5MeOH$ were isolated in the form of single crystals, the latter losing solvate on drying, to yield $2·2H_{2}O.$ Recrystallisation of $3·6H_{2}O$ in MeCN / MeOH also generates single crystals of $3·H_{2}O·2MeOH·2MeCN.$ Their X-ray characterisation shows that these Ni $_{6}$ clusters can be considered to be built from two triangular trinuclear [Ni $_{3}L$ $^{n}(OAc)(OH)]$ $^{+}$ subunits with different connectors. In addition, these studies demonstrate that the (L $^{n})$ $^{3}$ $^{−}$ ligands behave as trinucleating, adopting such a conformation that induces chirality in the isolated compounds. In this way, $3·H_{2}O·2MeOH·2MeCN$ appears particularly interesting, since it emerges as homochiral after undergoing spontaneous resolution upon crystallisation . The magnetic characterisation of $1·7.5H_{2}O$ to $3·6H_{2}O$ reveals that the three compounds present an overall antiferromagnetic coupling. The intricate magnetic behaviour of these clusters , mediated by a total of 14 bridges of different kinds, was analysed and satisfactorily interpreted in light of DFT calculations.
ISSN	14779226
Issue Number	45
Volume Number	39
e-ISSN	13645447
Journal	Dalton Trans.
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2010-12-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Magnetics Nickel Chemistry Organometallic Compounds Chemical Synthesis Quantum Theory Electron Spin Resonance Spectroscopy Models, Molecular Molecular Conformation Stereoisomerism X-Ray Diffraction Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

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