Search results for "singlet"
showing 10 items of 352 documents
Synthesis and crystal structure of the low-spin iron(II) complex [Fe(bpz)3](ClO4)2·H2O (bpz=2,2′-bipyrazine)
2004
Abstract The crystal structure of the title compound [Fe(bpz) 3 ](ClO 4 ) 2 · H 2 O (bpz=2,2 ′ -bipyrazine) has been determined by a single crystal X-ray diffraction study at 293(2) K. The complex is monoclinic, P 2 1 / c , a =17.263(3), b =9.983(2), c =17.921(4) A, β =107.94(3)°, V =2938.3(10) A 3 , Z =4, R =0.073 and R w =0.118. The structure is made up of tris-chelated [Fe(bpz) 3 ] 2+ cations, uncoordinated perchlorate anions and crystallization water molecules. The iron atom exhibits a FeN 6 distorted octahedral geometry with average Fe–N bond length and N–Fe–N bidentate angle of 1.962(5) A and 81.6(2)°. The value of the Fe–N bond distance and that of the room temperature magnetic mome…
Topological control of the spin coupling in dinuclear copper(II) complexes with meta- and para-phenylenediamine bridging ligands
2010
Abstract A novel series of copper(II) complexes of formula [Cu(tren)(mpda)](ClO4)2 · 1/2H2O (1), [Cu2(tren)2(mpda)](ClO4)4 · 2H2O (2), and [Cu2(tren)2(ppda)](ClO4)4 · 2H2O (3) containing the tetradentate tris(2-aminoethyl)amine (tren) terminal ligand and the potentially bridging 1,n-phenylenediamine [n = 3 (mpda) and 4 (ppda)] ligand have been prepared and spectroscopically characterized. X-ray diffraction on single crystals of 1 and 3 show the presence of mono- (1) and dinuclear (3) copper(II) units where the mpda (1) and ppda (3) ligands adopt terminal monodentate (1) and bridging bis(monodentate) (3) coordination modes toward [Cu(tren)]2+ cations with an overall non-planar, orthogonal di…
A new mixed-valence hexanuclear cobalt complex, [Co4IICo2III(dea)2(Hdea)4)(piv)4](ClO4)2·H2O: Synthesis, crystal structure and magnetic properties
2010
A new Co II /Co III hexanuclear complex, [Co 4 II Co 2 III (dea) 2 (Hdea) 4 )(piv) 4 ](ClO 4 ) 2 ·H 2 O 1 , has been obtained by reacting cobalt(II) perchlorate, diethanolamine, and pivalic acid (H 2 dea = diethanolamine and piv = pivalato anion). The cobalt ions are held together by four μ 3 and four μ 2 alkoxo bridges as well as by four syn – syn carboxylato groups. The hexanuclear motif contains four Co(II) and two Co(III) ions. The {Co II 4 Co III 2 (μ 2 -O) 4 (μ 3 -O) 4 } core can be described as a four face-sharing monovacant and bivacant distorted heterocubane units. The cobalt(III) ions are hexacoordinated. Two of the cobalt(II) are hexacoordinated, while the two others are pentacoo…
Computational chemistry meets experiments for explaining the geometry, electronic structure, and optical properties of Ca10V6O25
2018
In this paper, we present a combined experimental and theoretical study to disclose, for the first time, the structural, electronic, and optical properties of Ca10V6O25 crystals. The microwave-assisted hydrothermal (MAH) method has been employed to synthesize these crystals with different morphologies, within a short reaction time at 120 °C. First-principle quantum mechanical calculations have been performed at the density functional theory level to obtain the geometry and electronic properties of Ca10V6O25 crystal in the fundamental and excited electronic states (singlet and triplet). These results, combined with the measurements of X-ray diffraction (XRD) and Rietveld refinements, confirm…
Experimental and theoretical study of the energetic, morphological, and photoluminescence properties of CaZrO3:Eu3+
2018
In this study, we present a combined experimental and theoretical study of the geometry, electronic structure, morphology, and photoluminescence properties of CaZrO3:Eu3+ materials. The polymeric precursor method was employed to synthesize CaZrO3:Eu3+ crystals, while density functional theory calculations were performed to determine the geometrical and electronic properties of CaZrO3:Eu3+ in its ground and excited electronic states (singlet and triplet). The results were combined with X-ray diffraction (XRD) measurements to elucidate the local structural changes induced by the introduction of Eu3+ in the crystal lattice. This process results in the formation of intermediate levels in the ba…
Mechanism of photoluminescence in intrinsically disordered CaZrO3 crystals: First principles modeling of the excited electronic states
2017
Abstract CaZrO3 (CZO) powders obtained by the polymeric precursor method at 400 °C, and then, the samples were annealed at different temperatures (400, 600, 800, and 1000 °C) and characterized by X-ray diffraction, Raman and ultraviolet–visible spectroscopic methods, along with photoluminescence (PL) emissions. First principle calculations based on the density functional theory (DFT), using a periodic cell models, provide a theoretical framework for understanding the PL spectra based on the localization and characterization of the ground and electronic excited states. Fundamental (singlet, s ) and excited (singlet, s* , and triplet, t* ) electronic states were localized and characterized us…
<title>Coumarin fluorescent probes by electro-optical and laser spectrofluorimetry methods</title>
1997
Modified electro-optical absorption and emission methods were used to measure the dipole moments of six coumarin fluorescent probes (CU1, CU4, CU7, CU30, CU120, CU334) in the equilibrated ground, excited Franck-Condon and equilibrated excited states. The measurements were performed in cyclohexane and dioxane at room temperature. The equilibrated ground and excited states dipole measured by electro-optical methods are compared with those derived from other measurements techniques and from semiempirical calculations. Experiments and calculations performed in this work reveal a set of anomalous and interesting properties of CU7 and CU30 in solutions. The spectral dependence of some electro-opt…
Elektrooptische Emissionsuntersuchungen, III. Das Dipolmoment von trans-p-Dimethylamino-p′-nitrostilben im ersten angeregten Singulettzustand
1977
Aus elektrooptischen Emissions- und Absorptionsuntersuchungen in flussigen und glasig erstarrten Losungen kombiniert mit dielektrischen Untersuchungen konnten u. a. das Dipolmoment und die Polarisierbarkeitskomponente in Richtung des Dipolmoments von trans-p-Dimethylamino-p′-nitrostilben (DMANS) im ersten angeregten Singulettzustand bestimmt werden zu μ0a = (63 ± 5) · 10−30 Cm und α0az = (442 ± 65) · 10−40 CV−1 m2. Es zeigte sich, das die elektrooptischen Absorptions- und Emissionsuntersuchungen an DMANS in unpolaren Losungen zu einem konsistenten Satz von Dipolmomenten fuhren, das also die Aquilibrierung mit der Umgebung nach Anre-gung im unpolaren Cyclohexan keinen Einflus auf das permane…
Electronic structure of the glyoxalbis(2-hydroxyanil) (gha) ligand in [CoIII(gha)(PPh3)2]+: radical vs. non-radical states
2008
The synthesis, structure and spectroscopic properties of a complex salt [CoIII(gha)(PPh3)2][CoIICl3(PPh3)]·C2H5OH (1) are reported; gha = glyoxalbis(2-hydroxyanil). This is the first single crystal X-ray structure of a (gha)2− complex with a transition element. Though the determined bond parameters and UV-Vis spectroscopic data correlate well with a diradical description for the cation in 1, detailed electronic structure calculations using density functional theory confirm that [Co(gha)(PPh3)2]+ can be described as a closed shell singlet species which nevertheless displays an interesting electronic structure with significant electron transfer to the formally unoccupied LUMO of the square pl…
C3v Top Data System (C3vTDS) software for spectrum simulation of XY3Z symmetric-top molecules using the group chain
2010
Abstract The C3v Top Data System (C3vTDS) program suite has been developed with the aim of studying any rovibrational band or polyad of XY3Z (C3v) symmetric-tops molecules in a singlet electronic state. It is developed in the same way as similar programs for various molecular symmetries (Td, Oh, C4v, C2v and D2h). We work in the O ( 3 ) ⊃ C ∞ v ⊃ C 3 v group chain and this choice has consequences on the method used to specify the input parameters for Hamiltonian and transition moment calculations. One example concerning the ν 2 band of the CH 3 12 D symmetric-top molecule is presented. This package consists in a series of FORTRAN programs called by scripts. The whole package is freely acces…