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Author: Monakhov, Kirill Yu. × DDC: 540 ×

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    Polyoxometalates as components of supramolecular assemblies
    (Cambridge : RSC, 2019) Stuckart, Maria; Monakhov, Kirill Yu.
    The non-covalent interaction of polyoxometalates (POMs) with inorganic- or organic-based moieties affords hybrid assemblies with specific physicochemical properties that are of high interest for both fundamental and applied studies, including the discovery of conceptually new compounds and unveiling the impact of their intra-supramolecular relationships on the fields of catalysis, molecular electronics, energy storage and medicine. This minireview summarises the recent advances in the synthetic strategies towards the formation of such non-covalent POM-loaded assemblies, shedding light on their key properties and the currently investigated applications. Four main emerging categories according to the nature of the conjugate are described: (i) POMs in metal-organic frameworks, (ii) POMs merged with cationic metal complexes, (iii) architectures generated with solely POM units and (iv) POMs assembled with organic molecular networks. © 2019 The Royal Society of Chemistry.
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    Conductive Self-Assembled Monolayers of Paramagnetic {CoIICo4III} and {Co4IICo2III} Coordination Clusters on Gold Surfaces
    (Lausanne : Frontiers Media, 2019) Schmitz, Sebastian; Qiu, Xinkai; Glöß, Maria; van Leusen, Jan; Izarova, Natalya V.; Nadeem, Muhammad Arif; Griebel, Jan; Chiechi, Ryan C.; Kögerler, Paul; Monakhov, Kirill Yu.
    Two polynuclear cobalt(II,III) complexes, [Co5(N3)4(N-n-bda)4(bza·SMe)2] (1) and [Co6(N3)4(N-n-bda)2(bza·SMe)5(MeOH)4]Cl (2), where Hbza·SMe = 4-(methylthio)benzoic acid and N-n-H2bda = N-n-butyldiethanolamine, were synthesized and fully characterized by various techniques. Compound 1 exhibits an unusual, approximately C2-symmetric {CoII Co4II } core of two isosceles Co3 triangles with perpendicularly oriented planes, sharing a central, high-spin CoII ion residing in a distorted tetrahedral coordination environment. This central CoII ion is connected to four outer, octahedrally coordinated low-spin CoIII ions via oxo bridges. Compound 2 comprises a semi-circular {Co4IICo2III } motif of four non-interacting high-spin CoII and two low-spin CoIII centers in octahedral coordination environments. Self-assembled monolayers (SAMs) of 1 and 2 were physisorbed on template-stripped gold surfaces contacted by an eutectic gallium-indium (EGaIn) tip. The acquired current density-voltage (I-V) data revealed that the cobalt-based SAMs are more electrically robust than those of the previously reported dinuclear {CuIILnIII} complexes with Ln = Gd, Tb, Dy, or Y (Schmitz et al., 2018a). In addition, between 170 and 220°C, the neutral, mixed-valence compound 1 undergoes a redox modification, yielding a {Co5}-based coordination cluster (1-A) with five non-interacting, high-spin octahedral CoII centers as indicated by SQUID magnetometry analysis in combination with X-ray photoelectron spectroscopy and infrared spectroscopy. Solvothermal treatment of 1 results in a high-nuclearity coordination cluster, [Co10(N3)2(N-n-bda)6(bza·SMe)6] (3), containing 10 virtually non-interacting high-spin CoII centers. © Copyright © 2019 Schmitz, Qiu, Glöß, van Leusen, Izarova, Nadeem, Griebel, Chiechi, Kögerler and Monakhov.