M(II)(H₂O)₂ (5,5′-dimethyl-2,2′-bipyridine)(fumarato) [M = Co and Zn] complexes bearing a unique distorted trigonal-prismatic geometry and displaying 2D supramolecular structures

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• 作者：Antonio Té ; llez-Ló ; pez^a ; Jonathan Jaramillo-Garcí ; a^a ; Rogelio Martí ; nez-Domí ; nguez^a ; Raú ; l A. Morales-Luckie^b ; Miguel A. Camacho-Lopez^c ; Roberto Escudero^d ; Ví ; ctor Sá ; nchez-Mendieta^a ; ^{vsanchezm@uaemex.mx" class="auth_mail" title="E-mail the corresponding author}
• 关键词：Cobalt complexes ; Zinc complexes ; Trigonal-prismatic geometry ; Supramolecular network ; Fumarato
• 刊名：Polyhedron
• 出版年：2015
• 出版时间：4 November 2015
• 年：2015
• 卷：100
• 期：Complete
• 页码：373-381
• 全文大小：1619 K

文摘

Novel M(II)(H₂O)₂(dbpy)(fum) complexes, M = Co (1) and M = Zn (2); where: dbpy = 5,5′-dimethyl-2,2′-bipyridine, fum = fumarato; were obtained by simple one-pot solution reactions at ambient conditions, and structurally characterized by elemental analysis, IR spectroscopy and X-ray single crystal diffraction. In both complexes, the Co(II) and Zn(II) ions exhibit an uncommon six-coordinated distorted trigonal-prismatic geometry, especially for complexes having mono-dentate and bi-dentate innocent ligands. These are the first examples of metaprism complexes with aqua ligands in their coordination spheres. Moreover, the η¹:η¹ non-bridging coordination mode of fumarato ligand appears for the first time in these type of mononuclear complexes. In addition, the solid-state self-assembly of the mononuclear structures of 1 and 2, mainly throughout hydrogen bonding, give rise to 2D supramolecular wrinkle-sheet type frameworks. These extended structures seem to be the driving force for the unusual coordination geometry obtained in both complexes. Magnetic properties measurements reveal that complex 1 exhibits weak antiferromagnetic ordering with θ_(C–W) = −14 K and an E₁ = 0.24 cm⁻¹ according to Curie–Weiss model and Rueff phenomenological approach, respectively; whereas, complex 2 displays blue fluorescence in the solid-state.