Synthesis, structural, and physicochemical characterization of a Ti6 and a unique type of Zr6 oxo clusters bearing an electron-rich unsymmetrical {OON} catecholate/oxime ligand and exhibiting metalloaromaticity. Inorganic Chemistry, 59(24), pp. 18345-18357.
Abstract:Utilizing new experimental approaches and gradual understanding of the underlying chemical processes has led to advances in the self-assembly of inorganic and metal-organic compounds at a very fast pace over the last decades. Exploitation of unveiled information originating from initial experimental observations has sparked the development of new families of compounds with unique structural characteristics and functionalities. The main source of inspiration for numerous research groups originated from the implementation of the design element along with the discovery of new chemical components which can self-assemble into complex structures with wide range of sizes, topologies and functionalities. Not only do self-assembled inorganic and metal-organic chemical systems belong to families of compounds with configurable structures, but also have a vast array of physical properties which reflect the chemical information stored in the various "modular" molecular subunits. The purpose of this short review article is not the exhaustive discussion of the broad field of inorganic and metal-organic chemical systems, but the discussion of some representative examples from each category which demonstrate the implementation of new synthetic approaches and design principles.
Reaction of the oxidovanadium(IV)–LN–N species (LN–N is bipy = 2,2′-bipyridine
or bipy-like molecules) with either BF4
– or HF and/or KF results in the formation of compounds of the general
formula cis-[VIV(O)(F)(LN–N)2]+. Structural and spectroscopic (electron
paramagnetic resonance) characterization shows that these compounds
are in the tetravalent oxidation state containing a terminal fluorido
ligand. Density functional theory calculations reveal that the VIV–F bond is mainly electrostatic, which is reinforced
by reactivity studies that demonstrate the nucleophilicity of the
fluoride ligand in a halogen exchange reaction and in fluorination
of various organic substrates.
The hydrolytically stable dioxime ligand (2Ζ-6Ζ)-piperidine-2,6-dione (H3pidiox), acts as a strong chelator mainly with hard metals in high oxidation states, a pre-requisite for potential applications in metal sequestering processes from...
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