A5067260222- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Magnetism in coordination complexes
- Advanced Chemical Physics Studies
- Metal complexes synthesis and properties
- Metal-Catalyzed Oxygenation Mechanisms
- Crystallography and molecular interactions
- Hydrogen Storage and Materials
- Computational Drug Discovery Methods
- Lanthanide and Transition Metal Complexes
- Free Radicals and Antioxidants
- Spectroscopy and Quantum Chemical Studies
- Atomic and Molecular Physics
- Porphyrin and Phthalocyanine Chemistry
- Organometallic Complex Synthesis and Catalysis
- Graphene research and applications
- Organic and Molecular Conductors Research
- Electrocatalysts for Energy Conversion
- Electron Spin Resonance Studies
- Machine Learning in Materials Science
- Inorganic Chemistry and Materials
- Ammonia Synthesis and Nitrogen Reduction
- Quantum, superfluid, helium dynamics
- Nonlinear Optical Materials Research
- Metal-Organic Frameworks: Synthesis and Applications
Slovak University of Technology in Bratislava
2016-2025
Institute of Food Science and Technology
2018
Pacific Northwest National Laboratory
2012
Czech Academy of Sciences, Institute of Chemical Process Fundamentals
2010
Institute of Molecular Science and Technologies
2010
Abstract Crystallography and quantum mechanics have always been tightly connected because reliable mechanical models are needed to determine crystal structures. Due this natural synergy, nowadays accurate distributions of electrons in space can be obtained from diffraction scattering experiments. In the original definition crystallography (QCr) given by Massa, Karle Huang, direct extraction wavefunctions or density matrices measured intensities reflections or, conversely, ad hoc calculations...
This study investigates the possibility of detecting relativistic effects and electron correlation in single-crystal X-ray diffraction experiments using examples diphenyl mercury (HgPh2) triphenyl bismuth (BiPh3). In detail, importance (ECORR), (REL) [distinguishing between total, scalar spin–orbit (SO) coupling effects] picture change error (PCE) on theoretical density, its topology Laplacian infinite order two component (IOTC) wave functions is discussed. to develop an understanding...
Cobalt complexes with multiproton- and multielectron-responsive ligands are of interest for challenging catalytic transformations. The chemical redox noninnocence pentane-2,4-dione bis(S-methylisothiosemicarbazone) (PBIT) in a series cobalt has been studied by range methods, including spectroscopy [UV–vis, NMR, electron paramagnetic resonance (EPR), X-ray absorption (XAS)], cyclic voltammetry, diffraction, density functional theory (DFT) calculations. Two [CoIII(H2LSMe)I]I [CoIII(LSMe)I2]...
The experimental electron density distributions in two coordination compounds – one with a central Cu(I) atom and the other Cu(II), coordinated by same biphenyldiimino dithioether ( bite ) type of ligand have been obtained from high-resolution X-ray reflection data to model possible predisposition for redox reaction blue copper proteins. has adapted conformation required atom.
To study the experimental electronic structure, exact position of nonhydrogen atoms in starting geometry is necessary. In this paper, we compare results structure obtained using full data set [low-order (sinθ/λ < 0.7 Å −1 ) together with high-order > diffraction data] and based on low-order reflections only. The initial atomic displacement parameters were from NospherA2 software when data. If approach meaningful, it reduces measurement to acquisition time by a factor 7:1. Thus showing...
High-oxidation-state metal complexes with multiply bonded ligands are of great interest for both their reactivity as well fundamental bonding properties. This paper reports a combined spectroscopic and theoretical investigation into the effect apical ligand on spin-state preferences threefold symmetric iron(IV) tris(carbene) donor ligands. Specifically, singlet (S = 0) nitrido [{PhB(ImR)3}FeN], R tBu (1), Mes (mesityl, 2) related triplet 1) imido complexes, [{PhB(ImR)3}Fe(NR′)]+, Mes, R′...
With the aim of enhancing biological activity ruthenium-nitrosyl complexes, new compounds with four equatorially bound indazole ligands, namely, trans-[RuCl(Hind)4(NO)]Cl2·H2O ([3]Cl2·H2O) and trans-[RuOH(Hind)4(NO)]Cl2·H2O ([4]Cl2·H2O), have been prepared from trans-[Ru(NO2)2(Hind)4] ([2]). When pH-dependent solution behavior [3]Cl2·H2O [4]Cl2·H2O was studied, two complexes deprotonated ligands were isolated, namely [RuCl(ind)2(Hind)2(NO)] ([5]) [RuOH(ind)2(Hind)2(NO)] ([6]). All...
The extension of the X-ray constrained (XC) wavefunction approach to open-shell systems using unrestricted Hartree-Fock formalism is reported. XC method also extended include relativistic effects scalar second-order Douglas-Kroll-Hess approach. on charge and spin density two model compounds containing copper iron atom are size investigated in real reciprocal space; addition, picture-change discussed for isolated Cu atom. It found that terms lead changes densities much smaller than those from...
Abstract Graphene-based materials modified with transition metals, and their potential utilization as hydrogen storage devices, are extensively studied in the last decades. Despite this widespread interest, a comprehensive understanding of intricate interplay between graphene-based metal systems H 2 molecules remains incomplete. Beyond fundamental adsorption, activation molecule, crucial for catalytic reactions hydrogenation processes, may occur on center. In study, binding modes...
The redox properties of copper, nickel, and cobalt complexes (MePh3P)[M(bdt)2] with the ligand benzene-1,2-dithiolate (bdt) synthesized (MePh3P)[M(bdtCl2)2] 3,6-dichlorobenzene-1,2-dithiolate (bdtCl2) have been studied by cyclic voltammetry in situ EPR–UV/vis/NIR spectroelectrochemistry. addition chlorine substituents to 3- 6-positions benzene ring not only facilitates reduction [M(bdtCl2)2]− but also leads remarkable stabilization [M(bdtCl2)2]2– dianions solution. In contrast EPR-silent...
Mononuclear nickel(II), copper(II), and manganese(III) complexes with a noninnocent tetradentate Schiff base ligand containing disiloxane unit were prepared in situ by reaction of 3,5-di-tert-butyl-2-hydroxybenzaldehyde 1,3-bis(3-aminopropyl)tetramethyldisiloxane followed addition the appropriate metal(II) salt. The H2L resulting from these reactions is 2:1 condensation product 1,3-bis(3-aminopropyl)tetramethyldisiloxane. metal complexes, NiL·0.5CH2Cl2, CuL·1.5H2O, MnL(OAc)·0.15H2O,...
Quantum crystallographic refinement of heavy-element-containing compounds is a challenge, because many physical effects have to be accounted for adequately. Here, the impact and magnitude relativistic are compared with those electron correlation, polarization through environment, choice basis set treatment thermal motion on structure factors diphenylmercury(II) [Hg(Ph) 2 ] dicyanomercury(II) [Hg(CN) ]. Furthermore, individual atomic contributions explored in detail (using Mulliken population...
Biological activity, functionality, and synthesis of (fluoro)quinolones is closely related to their precursors (for instance 3-fluoroanilinoethylene derivatives) (i.e., functional groups, conformational behavior, and/or electronic structure). Herein, the theoretical study derivatives presented. Impact substituents (acetyl, methyl ester, ethyl ester) on analysis spectral behavior investigated. The B3LYP/6-311++G** computational protocol utilized. It found that intramolecular hydrogen bond...
This paper reports a systematic comparison of the performance alternative methods including relativistic effects on nature metal-metal bonding in Re2Cl8(2-) anion. The involved description using scalar Douglas-Kroll-Hess (DKH2) Hamiltonian with all-electron basis sets and effective core potential (ECP) sets. impact above picture was analyzed so-called domain averaged Fermi holes (DAFH). Besides comparing two methods, focus also put "exact" AIM generalized form DAFH analysis approximate...
A series of Mn(II) complexes differently substituted pyridinophane ligands, (Py2NR2)MnCl2 (R = iPr, Cy) and [(Py2NR2)MnF2](PF6) Cy, tBu) are synthesized characterized. The electrochemical properties these investigated by cyclic voltammetry, along with those previously reported (Py2NMe2)MnCl2 the Mn(III) complex [(Py2NMe2)MnF2](PF6). electronic structure this other is probed experimentally theoretically, via high-frequency -field electron paramagnetic resonance (HFEPR) spectroscopy ab initio...
Quantum chemical calculations reproduced well the electronic absorption spectrum and spin Hamiltonian parameters for MnL(NCS).
Nickel(II) complexes with 15-membered (1–5) and 14-membered (6) octaazamacrocyclic ligands derived from 1,2- 1,3-diketones S-methylisothiocarbohydrazide were prepared by template synthesis. The compounds characterized elemental analysis, electrospray ionization mass spectrometry, IR, UV–vis, 1H NMR spectroscopies, X-ray diffraction. contain a low-spin nickel(II) ion in square-planar coordination environment. electrochemical behavior of 1–6 was investigated detail, the electronic structure...
Abstract The ground state potential curves of the Zn 2 , Cd and Hg dimers calculated at different levels theory are presented compared with each other as well experimental theoretical studies. calculations level Dirac‐Coulomb Hamiltonian (DCH), 4‐component spin‐free Hamiltonian, nonrelativistic Lévy–Leblond simple Coulombic correction to DCH presented. in an all‐electron supermolecular approach including basis set superposition error (BSSE). Electron correlation is treated coupled cluster...
Abstract The study reported herein focused on the electronic structure of {Ru(NO)} 6 fragment and characterization oxidation state ruthenium in mer , trans ‐[RuCl 3 (Hind) 2 (NO)] ( 1 ; Hind = H ‐indazole) resulting from reaction (H O)(Hind) ] ) with NO acetone or solid‐state Anderson rearrangement ind) [RuCl 5 at 180 °C. results X‐ray diffraction, H, 13 C, 15 N NMR, EPR, IR, UV/Vis spectroscopy, cyclic voltammetry, magnetic susceptibility, XANES/EXAFS as well theoretical data have been...