Search results for "Unpaired electron"
showing 10 items of 60 documents
On the Road to MM′X Polymers: Redox Properties of Heterometallic Ni···Pt Paddlewheel Complexes
2014
On the quest of heterometallic mixed-valence MM'X chains, we have prepared two stable discrete bimetallic compounds: the reduced (PPN)[ClNi(μ-OSCPh)4Pt] (PPN = bis(triphenylphosphine)iminium; OSCPh = benzothiocarboxylato) and the oxidized [(H2O)Ni(μ-OSCPh)4PtCl] species. The role of the aqua and chlorido axial ligands is crucial to facilitate oxidation of the {Ni(μ-OSCPh)4Pt} core. Experimental and theoretical analyses indicate that a NiPt-Cl/Cl-NiPt isomerization process occurs in the oxidized species. The electronic structure of the reduced system shows two unpaired electrons, one located in a d(x(2)-y(2)) orbital of the Ni(II) ion and a second in the antibonding d(z(2)-dz(2)) combination…
Role of the Open-Shell Character on the Pressure-Induced Conductivity of an Organic Donor-Acceptor Radical Dyad
2018
Single‐component conductors based on neutral organic radicals have received a lot of attention due to the possibility that the unpaired electron can serve as a charge carrier without the need of a previous doping process. Although most of these systems are based on delocalized planar radicals, we present here a nonplanar and spin localized radical based on a tetrathiafulvalene (TTF) moiety, linked to a perchlorotriphenylmethyl (PTM) radical by a conjugated bridge, which exhibits a semiconducting behavior upon application of high pressure. The synthesis, electronic properties, and crystal structure of this neutral radical TTF‐Ph‐PTM derivative (1) are reported and implications of its crystal…
Synthesis, molecular structures and EPR spectra of the paramagnetic cuboidal clusters with Mo3S4Ga cores
2017
Electron precise [Mo3(l3-S)(l-S)3(diphos)3Br3]Br (diphos = dppe, dmpe) incomplete cuboidal clusters with six cluster skeletal electrons (CSE) were converted into paramagnetic cuboidal [Mo3(GaBr)(l3-S)4- (diphos)3Br3] clusters by treatment with elemental Ga. The new heterobimetallic complexes with nine CSE possess a doublet ground state with the unpaired electron density delocalized over the three molybdenum atoms.
Structural analysis of Cu(II) ligation to the 5'-GMP nucleotide by pulse EPR spectroscopy.
2007
JBIC Journal of Biological Inorganic Chemistry, 12 (6)
Short-range order and luminescence in amorphous silicon oxynitride
2000
Abstract Using Si 2p core-level X-ray photoelectron spectroscopy, we found that the short-range order in amorphous silicon oxynitride (a-SiOxNy) can be quantitatively described by a random bonding model. Results also show that the second and even further neighbours of the Si in the network affect the chemical shifts of the X-ray photoelectron spectra. Cathodoluminescence and photoluminescence of a-SiOxNy with different compositions are also measured. A red band with energies of 1.8–1.9 eV, a blue band with an energy of 2.7 eV and ultraviolet bands with energies of 13.1, 3.4–3.6, 4.4–4.7 and 5.4eV were observed. The 1.8–1.9 eV band is attributed to the O and N atoms with an unpaired electron…
New Tetrahydro-1,2,4,5-Tetrazinan-3-Ones and Oxoverdazyl Free Radicals
2006
A series of tetrahydro-1,2,4,5-tetrazinan-3-ones have been prepared by the reaction of carbonic acid bis (1-methylhydrazide) with aromatic aldehydes. These were oxidised to oxoverdazyl free radicals and used immediately for ESR spectroscopy studies that indicate that the unpaired electron is delocalised over the verdazyl ring. The ESR spectra can be very well simulated considering hyperfine couplings with the four nitrogen atoms of the verdazyl ring and the six hydrogen atoms of the two methyl groups bonded to it.
Electronic Structures and Spectroscopic Properties of 6π-Electron Ring Molecules and Ions E2N2 and E42+ (E = S, Se, Te)
2004
The electronic structures and molecular properties of square-planar 6π-electron ring molecules and ions E2N2 and E42+ (E = S, Se, Te) were studied using various ab initio methods and density functionals. All species were found to contain singlet diradical character in their electronic structures. Detailed analysis of the CAS wave function of S2N2 in terms of different valence bond structures gives the largest weight for a Lewis-type singlet diradical VB structure in which the two unpaired electrons reside on nitrogen atoms, though the relative importance of the different VB structures is highly dependent on the level of theory. The diradical character in both E2N2 and E42+ was found to incr…
Orbiting Orbitals: Visualization of Vi-Bronic Motion at a Conical Intersection
2013
The Jahn-Teller (JT) active unpaired electron of single metalloporphyrin radical anions is imaged through scanning tunneling microscopy. It is demonstrated that the electron is delocalized over the porphyrin macrocycle and its topographic image is determined by vibronic motion: the orbital of the electron adiabatically follows the zero-point pseudorotation of skeletal deformations. Transformation of the polar graphs of the observed images allows visualization of the adiabatic vibrational density to which the electron is coupled. The vibronic potential at the conical intersection is visualized and the half-integer angular momentum characteristic of the Berry phase is revealed in the radial f…
Paramagnetic aluminium β-diketiminate
2012
The β-diketiminate ligand framework is shown to undergo reduction to form a neutral main group radical stabilized by spiroconjugation of the unpaired electron over the group 13 element centre. The synthesized paramagnetic complex was characterized by EPR spectroscopy and computational chemistry.
A stable oxoverdazyl free radical: Structural and magnetic characterization
2006
Abstract The structure and magnetic properties (susceptibility and ESR) of the stable oxoverdazyl free radical 6-(4-acetamidophenyl)-1,4,5,6-tetrahydro-2,4-dimethyl-1,2,4,5-tetrazin-3(2H)-one are presented. The crystal structure consists of chains of parallel planar molecules running along the b-axis. These chains are formed by dimers with a ring-over-bond overlap and a significant offset between dimers, although with similar inter- and intradimer distances. The susceptibility measurements show that this compound is an S = 1/2 paramagnet with weak antiferromagnetic interactions. The magnetic susceptibility can be very well reproduced with an antiferromagnetic regular chain model with g = 2.…