Search results for "Singlet"
showing 10 items of 352 documents
Electron Fabry-Perot interferometer with two entangled magnetic impurities
2007
We consider a one-dimensional (1D) wire along which single conduction electrons can propagate in the presence of two spin-1/2 magnetic impurities. The electron may be scattered by each impurity via a contact-exchange interaction and thus a spin-flip generally occurs at each scattering event. Adopting a quantum waveguide theory approach, we derive the stationary states of the system at all orders in the electron-impurity exchange coupling constant. This allows us to investigate electron transmission for arbitrary initial states of the two impurity spins. We show that for suitable electron wave vectors, the triplet and singlet maximally entangled spin states of the impurities can respectively…
Synthesis of a labile sulfur-centred ligand, [S(H)C(PPh2S)2]−: structural diversity in lithium(i), zinc(ii) and nickel(ii) complexes
2016
A high-yield synthesis of [Li{S(H)C(PPh2S)2}]2 [Li2·(3)2] was developed and this reagent was used in metathesis with ZnCl2 and NiCl2 to produce homoleptic complexes 4 and 5b in 85 and 93% yields, respectively. The solid-state structure of the octahedral complex [Zn{S(H)C(PPh2S)2}2] (4) reveals notable inequivalence between the Zn-S(C) and Zn-S(P) contacts (2.274(1) Å vs. 2.842(1) and 2.884(1) Å, respectively). Two structural isomers of the homoleptic complex [Ni{S(H)C(PPh2S)2}2] were isolated after prolonged crystallization processes. The octahedral green Ni(ii) isomer 5a exhibits the two monoprotonated ligands bonded in a tridentate (S,S',S'') mode to the Ni(ii) centre with three distinctl…
DNA interaction of new copper(II) complexes with sulfonamides as ligands
2007
New copper(II) complexes with sulfonamide ligands have been prepared and characterized. Sulfonamide ligands were prepared through a reaction between 8-aminoquinoline and either 2-mesitylene (Hqmesa), 4-tert-butylbenzene (Hqtbsa), or alpha-toluene (Halphaqtsa) sulfonyl chlorides. The structural analysis carried out for complex [Cu(alphaqtsa)(2)] indicated that the local environment of the Cu(II) cation is between a square planar and a tetrahedral geometry, with stacking of the benzene rings of the sulfonyl ligands between neighbor molecules. Powder EPR spectra at room temperature gave rhombic spectra for the [Cu(alphaqtsa)(2)] and [Cu(qmesa)(2)] complexes and an axial spectrum for the [Cu(qt…
Phosphane tuning in heteroleptic [Cu(N^N)(P^P)]+ complexes for light-emitting electrochemical cells
2019
The synthesis and characterization of five [Cu(P^P)(N^N)][PF 6 ] complexes in which P^P = 2,7-bis( tert -butyl)-4,5-bis(diphenylphosphino)-9,9-dimethylxanthene ( t Bu 2 xantphos) or the chiral 4,5-bis(mesitylphenylphosphino)-9,9-dimethylxanthene (xantphosMes 2 ) and N^N = 2,2'-bipyridine (bpy), 6-methyl-2,2'-bipyridine (6-Mebpy) or 6,6'-dimethyl-2,2'-bipyridine (6,6'-Me 2 bpy) are reported. Single crystal structures of four of the compounds confirm that the copper(I) centre is in a distorted tetrahedral environment. In [Cu(xantphosMes 2 )(6-Mebpy)][PF 6 ], the 6-Mebpy unit is disordered over two equally populated orientations and this disorder parallels a combination of two dynamic processe…
A Computational Study of Ethylene C−H Bond Activation by [Cp*Ir(PR3)]
2001
It has previously been demonstrated that both [(C5Me5)Ir(PMe3)(CH=CH2)H] and [(C5Me5)Ir(PMe3)(H2C=CH2)] are formed when [(C5Me5)Ir(PMe3)] is thermolytically generated in the presence of ethylene. At higher temperatures, the vinyl hydride is converted to the eta2-ethylene adduct. Density functional theory has now been used to investigate this reaction, using the B3LYP functional, two types of basis sets (LanL2DZ and TZV*), and two models of the [(C5R5)Ir(PR3)] species (R=H and CH3). The study consists of full optimizations of local minima, first-order saddle points, and minimum energy crossing points (MECP). The experimental results are best accounted for by considering both singlet and trip…
Shape-persistent poly-porphyrins assembled by a central truxene: synthesis, structure, and singlet energy transfer behaviors
2013
Four dyad systems composed of a central truxene and either one or three β-substituted zinc(II) porphyrins (ZnP: TruZnP (7) and TruTriZnP (9)) or free-bases (H2P: TruP (6) and TruTriP (8)) have been prepared. The presence of β-methyl groups minimizes π-conjugation through the quasi right angle made by the porphyrin and the truxene planes, and renders these dyads relatively rigid. The position of the absorption and emission 0–0 peaks confirms the role of the truxene and porphyrin as the energy donor and acceptor, respectively. Selective excitation of the truxene results in an efficient singlet energy transfer (S1 ET) from the truxene to the porphyrin unit. The rates for S1 ET (k ET ) are ext…
DNA cleavage reaction induced by dimeric copper(II) complexes of N-substituted thiazole sulfonamides
2005
A new dinuclear copper(II) complex has been synthesised and structurally characterised: [Cu2(tz-ben)4] (Htz-ben = N-thiazol-2-yl-benzenesulfonamide). Its crystal structure, magnetic properties and electronic paramagnetic resonance (EPR) spectra were studied in detail. In the compound the metal centres are bridged by four non-linear triatomic NCN groups. The coordination geometry of the copper ions in the dinuclear entity is distorted square pyramidal (4+1). Two thiazole N and two sulfonamido N atoms occupy the equatorial positions and one sulfonamido O atom is in the axial position. Magnetic susceptibility data show a strong antiferromagnetic coupling, -2J = 114.1 cm(-1). The EPR spectra of…
Transport anisotropy and of thin films
2005
Abstract The resistivity R ( T ) of superconducting UNi 2 Al 3 thin films shows a pronounced dependence on the current direction. Specifically, the superconducting transition temperature T c is directional dependent as well as the influence of the magnetic ordering on the transport properties. Also the upper critical field B c 2 ( Θ , T ) is moderately influenced by the probe current direction. These anisotropies are discussed in the framework of multiband superconductivity. The initial slope of the upper critical field B c 2 ′ ( T ) provides evidence for a spin singlet state.
Electron and Energy Transfer Mechanisms: The Double Nature of TiO2 Heterogeneous Photocatalysis
2021
Photocatalytic chemical transformations in the presence of irradiated TiO2 are generally considered in terms of interfacial electron transfer. However, more elusive energy-transfer-driven reactions have been also hypothesized to occur, mainly on the basis of the indirect evidence of detected reaction products whose existence could not be justified simply by electron transfer. Unlike in homogeneous and colloidal systems, where energy transfer mechanisms have been investigated deeply for several organic syntheses, understanding of similar processes in heterogeneous systems is at only a nascent level. However, this gap of knowledge can be filled by considering the important achievements of syn…
Distinct photodynamics of κ-N and κ-C pseudoisomeric iron(ii) complexes
2021
Two closely related FeII complexes with 2,6-bis(1-ethyl-1H-1,2,3-triazol-4yl)pyridine and 2,6-bis(1,2,3-triazol-5-ylidene)pyridine ligands are presented to gain new insights into the photophysics of bis(tridentate) iron(II) complexes. The [Fe(N^N^N)2]2+ pseudoisomer sensitizes singlet oxygen through a MC state with nanosecond lifetime after MLCT excitation, while the bis(tridentate) [Fe(C^N^C)2]2+ pseudoisomer possesses a similar 3MLCT lifetime as the tris(bidentate) [Fe(C^C)2(N^N)]2+ complexes with four mesoionic carbenes. Financial support from the Deutsche Forschungsge-meinschaft [DFG, Priority Program SPP 2102] "Light-controlled reactivity of metal complexes" (BA 4467/7-1, LO 714/11-1, …