A5088100414- Crystallization and Solubility Studies
- X-ray Diffraction in Crystallography
- Synthesis and characterization of novel inorganic/organometallic compounds
- Boron and Carbon Nanomaterials Research
- Inorganic Chemistry and Materials
- Organometallic Complex Synthesis and Catalysis
- Synthesis and Properties of Aromatic Compounds
- Radioactive element chemistry and processing
- Lanthanide and Transition Metal Complexes
- Boron Compounds in Chemistry
- Advanced battery technologies research
- Crystallography and molecular interactions
- Hydrogen Storage and Materials
- Inorganic Fluorides and Related Compounds
- Advanced Chemical Physics Studies
- Graphene research and applications
- Magnetism in coordination complexes
- Electrocatalysts for Energy Conversion
- MXene and MAX Phase Materials
- Coordination Chemistry and Organometallics
- Electrochemical Analysis and Applications
- Fullerene Chemistry and Applications
- Chemical Synthesis and Characterization
- Crystal Structures and Properties
- 2D Materials and Applications
Peter the Great St. Petersburg Polytechnic University
2025
University of Akron
2022-2024
Washington State University
2024
Los Alamos National Laboratory
2018-2022
Los Alamos Medical Center
2020
Utah State University
2011-2018
Peoples' Friendship University of Russia
2017
Changchun Institute of Applied Chemistry
2016
State Key Laboratory of Rare Earth Resources Utilization
2016
University of Bremen
2015
Boron is an interesting element with unusual polymorphism. While three-dimensional (3D) structural motifs are prevalent in bulk boron, atomic boron clusters found to have planar or quasi-planar structures, stabilized by localized two-center-two-electron (2c-2e) σ bonds on the periphery and delocalized multicenter-two-electron (nc-2e) both π frameworks. Electron delocalization a result of boron's electron deficiency leads fluxional behavior, which has been observed B13(+) B19(-). A unique...
Two-dimensional (2D) materials with planar hypercoordinate motifs are extremely rare due to the difficulty in stabilizing configurations extended systems. Furthermore, such exotic often unstable. We predict a novel Cu2Si 2D monolayer featuring hexacoordinate copper and silicon. This is global minimum space which displays reduced dimensionality rule-breaking chemical bonding. system has been studied density functional theory, including molecular dynamics simulations electronic structure...
Abstract The electron deficiency and strong bonding capacity of boron have led to a vast variety molecular structures in chemistry materials science. Here we report the observation highly symmetric cobalt-centered drum-like CoB 16 − , characterized by photoelectron spectroscopy ab initio calculations. spectra display relatively simple spectral pattern, suggesting high symmetry structure. Two nearly degenerate isomers with D 8d ( I ) C 4v II symmetries are found computationally compete for...
Small boron clusters are known to be planar, and may used as ligands form novel coordination complexes with transition metals. Here we report a combined photoelectron spectroscopy ab initio study of CoB12– RhB12–. Photoelectron spectra the two doped-B12 show similar spectral patterns, suggesting they have structures. Global minimum searches reveal that both RhB12– possess half-sandwich-type structures quasi-planar B12 moiety coordinating metal atom. The ligand is found structure bare cluster...
The structure and chemical bonding of the 24-atom boron cluster are investigated using photoelectron spectroscopy ab initio calculations. joint experimental theoretical investigation shows that B24(-) possesses a quasi-planar containing fifteen outer nine inner atoms with six forming filled pentagonal moiety. central atom moiety is puckered out plane by 0.9 Å, reminiscent six-atom caps well-known B12 icosahedral unit. next closest isomer at ROCCSD(T) level theory has tubular double-ring...
We report the observation of a manganese-centered tubular boron cluster (MnB16−), which is characterized by photoelectron spectroscopy and ab initio calculations. The relatively simple pattern spectrum indicates to be highly symmetric. Ab calculations show that MnB16− has Mn-centered structure with C4v symmetry due first-order Jahn-Teller effect, while neutral MnB16 reduces C2v second-order effect. In MnB16−, two unpaired electrons are observed, one on Mn 3dz2 orbital another B16 tube,...
We predict a two-dimensional (2D) antiferromagnetic (AFM) boron (designated as $M$-boron) by using ab initio evolutionary methodology. $M$-boron is entirely composed of ${\mathrm{B}}_{20}$ clusters in hexagonal arrangement. Most strikingly, the highest valence band isolated, strongly localized, and quite flat, which induces spin polarization on either cap cluster. This flat originates from unpaired electrons capping atoms responsible for magnetism. thermodynamically metastable first magnetic...
Synthetic strategies to yield molecular complexes of high-valent lanthanides, other than the ubiquitous Ce4+ ion, are exceptionally rare, and thorough, detailed characterization in these systems is limited by complex lifetime reaction isolation conditions. The synthesis high-symmetry high purity with significant lifetimes solution solid state essential for determining role ligand-field splitting, multiconfigurational behavior, covalency governing reactivity physical properties potentially...
We predict two novel highly stable 2D planar hexacoordinate monolayer sheets Ni<sub>2</sub>Si and Ni<sub>2</sub>Ge with unusual chemical bonding.
Using quantum-chemical calculations and reduced dimensionality, we show that the "post-anti-van't Hoff-Le Bel" motif of germanium can be stabilized in a novel two-dimensional (2D) copper-germanium alloy film. This hypercoordinate sheet is first stable planar hexacoordinate material 2D space. First principle molecular dynamics indicate this Cu2Ge film diamagnetic metal, survives brief 10 ps annealing up to 1200 K. The electron delocalization chemical bonding are unique different from...
Copper has been shown to be an important substrate for the growth of borophenes. Copper-boron binary clusters are ideal platforms study interactions between copper and boron, which may provide insight about underlying mechanisms borophene on substrates. Here we report a joint photoelectron spectroscopy theoretical two copper-doped boron clusters, CuB7- CuB8-. Well resolved spectra obtained at different wavelengths used understand structures bonding properties CuBn- clusters. We find that...
Abstract Antiaromaticity, as introduced in 1965, usually refers to monocyclic systems with 4 n π electrons. This concept was extended all‐metal molecules after the observation of Li 3 Al − gas phase. However, solid‐phase counterparts have not been documented date. Herein, we describe a series antiaromatic anions, [Ln( η ‐Sb ) ] 3− (Ln=La, Y, Ho, Er, Lu), which were isolated K([2.2.2]crypt) salts and identified by single‐crystal X‐ray diffraction. Based on results obtained from chemical...
Photoelectron spectroscopy and ab initio calculations are used to investigate the structures chemical bonding of B25(-) cluster. Global minimum searches reveal a dense potential energy landscape with 13 quasi-planar within 10 kcal/mol at CCSD(T)/6-311+G(d) level theory. Three isomers (I, II, III) lowest in nearly degenerate CCSD(T) theory, II III being 0.8 0.9 higher, respectively, whereas two density functional levels theory isomer is (8.4 more stable than I PBE0/6-311+G(2df) level)....
A redox pair of Ce<sup>4+</sup> and Ce<sup>3+</sup> complexes, isotypic to previously prepared Tb<sup>4+</sup> Tb<sup>3+</sup> respectively, is reported establish a comparative physical spectroscopic analysis tetravalent lanthanide ions.
In all known examples of metal-ligand (M-L) δ and φ bonds, the metal orbitals are aligned to ligand in a "head-to-head" or "side-to-head" fashion. Here, we report two fundamentally new types M-L interactions; "head-to-side" "side-to-side" back-bonding, found complexes metallacyclopropenes metallacyclocumulenes actinides (Pa-Pu) that makes them distinct from their corresponding Group 4 analogues. addition Th U complexes, our calculations include Pa, Np, Pu. contrast with conventional An-C...
The study of the redox chemistry mid-actinides (U-Pu) has historically relied on cerium as a model, due to accessibility trivalent and tetravalent oxidation states for these ions. Recently, dramatic shifts lanthanide 4+/3+ non-aqueous couples have been established within homoleptic imidophosphorane ligand framework. Herein we extend (NPC=[N=Pt Bu(pyrr)2 ]- ; pyrr=pyrrolidinyl) tetrahomoleptic NPC complexes neptunium (1-M, 2-M, M=Np, Ce) present comparative structural, electrochemical,...
We report the synthesis and characterization of substituted aryldimethylsilyldiisopropylanilide ligands their respective bisamido complexes U(III), (3,5-R2-PhMe2SiNDipp)2UI(dioxane)x (1, R = H, x= 0; 2, Me, x 3, tBu, 1). found that steric bulk 3,5-R2-Ph ring affects hapticity U–arene interaction. In solid-state, 1 is a U–(η6-arene) complex, while 2 bis(U–(η1-arene)) complex. Theoretically calculated bond orders at PBE0 PBE0-D3 levels theory support these assignments. The 3,5-tBu2-Ph rings 3...
IX (X=O, N, C) bonding was analyzed in the related hypervalent iodine compounds based on adaptive natural density partitioning (AdNDP) approach. The results confirm presence of a I→X σ dative bond, as opposed to widely used IX notation. A clear formulation electronic structure these would be useful establishing reaction mechanisms and structures bioinorganic problems general applicability.
Abstract Gas‐phase clusters are deemed to be σ‐aromatic when they satisfy the 4 n +2 rule of aromaticity for delocalized σ electrons and fulfill other requirements known aromatic systems. While range values was shown quite broad applied short‐lived found in molecular‐beam experiments, stability all‐metal cluster‐like fragments isolated condensed phase previously mainly ascribed two ( =0). In this work, applicability concept is extended towards solid‐state compounds by demonstrating a unique...
We report the successful isolation and structural elucidation of two bimetallic doped [Co2 @Ge16 ]4- clusters (α β form), which were synthesized through reaction [{(ArN)2 CtBu}Co(η6 -toluene)] (Ar=2,6-diisopropylphenyl) K4 Ge9 in ethylenediamine (en) solution co-crystallized together [K(2,2,2-crypt)]4 ]⋅en. The α-[Co2 isomer prefers a distinct D2h 3-connected architecture, whereas deltahedral isomeric β-[Co2 adopts quasi-C2h geometry can be seen as coupling distorted arachno-[Co@Ge10 ]...