Copper(II) complexes with 1-phenyl-4,6-dimethylpyrimidine-2-thione. Chemical, spectroscopic, magnetic, conductivity and polarographic studies

1990 ◽  
Vol 55 (9) ◽  
pp. 2199-2215 ◽  
Author(s):  
Raffaele Battistuzzi ◽  
Marco Borsari
Keyword(s):  
Room Temperature ◽  
Copper Ions ◽  
Magnetic Moments ◽  
Thermal Analyses ◽  
Ligand Field ◽  
L System ◽  
Counter Ions ◽  
Ligand Field Spectra ◽  
Ir Bands ◽  
Magnetic Conductivity

New copper(II) complexes of general composition: CuLX2.nH2O (X = Cl-, n = 0.25; X = NO3-, n = 0.5), Cu2L3Cl4.2H2O, CuL2X2.H2O (X = ClO4-, BF4- and NO3-) and Cu2L7X4 (X = ClO4-, BF4- and NO3-), where L = 1-phenyl-4,6-dimethylpyrimidine-2-thione, have been isolated. Chemical and thermal analyses, conductivity, magnetic susceptibility, infrared and ligand field spectroscopic data and, for the perchlorate complexes also polarographic studies, are reported. Diagnostic IR bands frequencies of counter-ions, χ(Cu-X) modes and ligand field spectra for the mono-and bis-ligand compounds, having an equatorial [CuNSCl2], [CuNSO2] and [CuN2S2] microsymmetry, indicate a coordinating character of some anions, suggesting an elongated octahedral geometry for these complexes. For the [Cu2L7]X4 (X = ClO4-, BF4- and NO3-) complexes, which exhibit at room temperature subnormal magnetic moments, a polynuclear structure with the copper(II) in a roughly square-pyramidal environment, is proposed. Polarographic data for the perchlorate complexes and for the Cu(ClO4)2-L system at various ligand concentrations, have shown that in DMF solution the prevailing species are [CuL2]2+, [CuL3]2+ and [Cu2L7]4+ confirming the oxidation state II for the copper ions in the [Cu2L7]X4 complexes.

Copper(II) complexes of o-hydroxyarylcarbonyl compounds

1968 ◽  
Vol 21 (3) ◽  
pp. 617 ◽  
Author(s):  
DP Graddon ◽  
GM Mockler
Keyword(s):  
Solid State ◽  
Chelate Ring ◽  
Magnetic Moments ◽  
Equilibrium Constants ◽  
Ligand Field ◽  
Infrared Band ◽  
Planar Structures ◽  
Square Planar ◽  
Inductive Effects ◽  
Ligand Field Spectra

A series of copper(11) complexes has been prepared of the type CuL2Bn, where L is an o-hydroxy-aryl-, or naphthyl-, aldehyde, ketone, or ester, B is water or 4-methylpyridine, and n = 0, 1, or 2. All these complexes have a strong infrared band in the region 1600-1660 cm-l, showing that the oxygen atoms in the chelate ring are non-equivalent ; their magnetic moments fall in the range usual for copper(11) compounds. Equilibrium constants determined for the addition of one molecule of 4-methylpyridine to the anhydrous compounds in chloroform solutions fall in the range 0.5 < k < 40 and are comparable to the constant for the addition of 4-methylpyridine to bis(acetylacetonato)copper(11) (b 2.7). Increased stability of the adducts can be associated with the inductive effects of ligand substituents. Ligand field spectra in the solid state and in solution closely resemble those of corresponding bis(acetylaoetonato)copper(11) complexes and provide evidence for square-planar structures of the anhydrous complexes and square-pyramidal structures of the 1 : 1 adducts with 4-methylpyridine or water. No evidence is available for the structures of 1 : 2 adduots which may be formed in solutions in 4-methylpyridine; these solutions are unstable, but the nature of the slow reactions which occur in these solutions is not known.

Ligand-Field Calculations on Pseudo-Tetragonal High-Spin Fe(II) Compounds

1977 ◽  
Vol 32 (12) ◽  
pp. 1404-1418
Author(s):  
A. Vermaas ◽  
W. L. Groeneveld ◽  
J. Reedijk
Keyword(s):  
Experimental Data ◽  
Magnetic Susceptibility ◽  
Room Temperature ◽  
Point Group ◽  
Point Symmetry ◽  
Ligand Field ◽  
Ligand Field Theory ◽  
State Splitting ◽  
Ligand Field Spectra ◽  
Theoretical Results

Abstract The compounds Fe(pz)4X2 and Fe(mpz)4X2, where pz stands for pyrazole, mpz for 5-methyl-pyrazole and X means Cl, Br or I, have been investigated by magnetic susceptibility, magnetic saturation and Mössbauer spectroscopy. The experimental temperatures vary from 2K to room temperature for the magnetic susceptibility measurements and from 4K to room temperature for the Mössbauer measurements. Mössbauer spectra in an applied magnetic field are also reported. The results of both types of measurements and ligand-field spectra are interpreted using a ligand-field theory. The tetragonal ground-state splitting parameters have been determined using the ligand-field spectra. For the pyrazole compounds, the experimental data nicely agree with theoretical results. The quadrupole splitting and the magnetic properties of these com­ pounds can be completely described within the used model, assuming a tetragonal molecular point symmetry. For the 5-methylpyrazole compounds, the measurements show that the point symmetry is lower than tetragonal. The agreement between the experimental data and the theoretical results for a point group Ci is less fair, especially concerning the Vzz and η values. Besides the Vzz values of Fe(mpz)4X2 differ significantly from those of the corresponding Fe(pz)4X2 compounds.

Some complexes of Fe(II) with thiourea ligands

1967 ◽  
Vol 45 (10) ◽  
pp. 1135-1142 ◽  
Author(s):  
R. A. Bailey ◽  
Terry Roy Peterson
Keyword(s):  
Infrared Spectra ◽  
Sulfur Atom ◽  
Magnetic Moments ◽  
The Other ◽  
Ligand Field ◽  
Thiocyanate Ion ◽  
Ligand Field Spectra

Fe(thiourea)2(SCN)2, Fe(thiourea)4Cl2, and FeL2Cl2 (where L = methylthiourea, 1,3-dimethylthiourea, and 1,3-diethylthiourea) have been prepared and characterized. Magnetic moments and ligand field spectra indicate that all are octahedral. Infrared spectra show that the thiourea and methylthiourea ligands coordinate through the sulfur atom; the other two ligands are probably sulfur bonded also. The thiocyanate ion is coordinated through the nitrogen.

Intrinsic doping limit and defect-assisted luminescence in Cs4PbBr6

2019 ◽  
Author(s):  
Young-Kwang Jung ◽  
Joaquin Calbo ◽  
Ji-Sang Park ◽  
Lucy D. Wahlley ◽  
Sunghyun Kim ◽  
...  
Keyword(s):  
First Principles ◽  
Room Temperature ◽  
Stokes Shift ◽  
Green Luminescence ◽  
Counter Ions ◽  
Self Consistent ◽  
Deep Ultraviolet ◽  
Halide Perovskite ◽  
Related Compounds ◽  
Level Analysis

Cs<sub>4</sub>PbBr<sub>6 </sub>is a member of the halide perovskite family that is built from isolated (zero-dimensional) PbBr<sub>6</sub><sup>4-</sup> octahedra with Cs<sup>+</sup> counter ions. The material exhibits anomalous optoelectronic properties: optical absorption and weak emission in the deep ultraviolet (310 - 375 nm) with efficient luminescence in the green region (~ 540 nm). Several hypotheses have been proposed to explain the giant Stokes shift including: (i) phase impurities; (ii) self-trapped exciton; (iii) defect emission. We explore, using first-principles theory and self-consistent Fermi level analysis, the unusual defect chemistry and physics of Cs<sub>4</sub>PbBr<sub>6</sub>. We find a heavily compensated system where the room-temperature carrier concentrations (< 10<sup>9</sup> cm<sup>-3</sup>) are more than one million times lower than the defect concentrations. We show that the low-energy Br-on-Cs antisite results in the formation of a polybromide (Br<sub>3</sub>) species that can exist in a range of charge states. We further demonstrate from excited-state calculations that tribromide moieties are photoresponsive and can contribute to the observed green luminescence. Photoactivity of polyhalide molecules is expected to be present in other halide perovskite-related compounds where they can influence light absorption and emission. <br>

Intrinsic doping limit and defect-assisted luminescence in Cs4PbBr6

2019 ◽  
Author(s):  
Young-Kwang Jung ◽  
Joaquin Calbo ◽  
Ji-Sang Park ◽  
Lucy D. Wahlley ◽  
Sunghyun Kim ◽  
...  
Keyword(s):  
First Principles ◽  
Room Temperature ◽  
Stokes Shift ◽  
Green Luminescence ◽  
Counter Ions ◽  
Self Consistent ◽  
Deep Ultraviolet ◽  
Halide Perovskite ◽  
Related Compounds ◽  
Level Analysis

Cs<sub>4</sub>PbBr<sub>6 </sub>is a member of the halide perovskite family that is built from isolated (zero-dimensional) PbBr<sub>6</sub><sup>4-</sup> octahedra with Cs<sup>+</sup> counter ions. The material exhibits anomalous optoelectronic properties: optical absorption and weak emission in the deep ultraviolet (310 - 375 nm) with efficient luminescence in the green region (~ 540 nm). Several hypotheses have been proposed to explain the giant Stokes shift including: (i) phase impurities; (ii) self-trapped exciton; (iii) defect emission. We explore, using first-principles theory and self-consistent Fermi level analysis, the unusual defect chemistry and physics of Cs<sub>4</sub>PbBr<sub>6</sub>. We find a heavily compensated system where the room-temperature carrier concentrations (< 10<sup>9</sup> cm<sup>-3</sup>) are more than one million times lower than the defect concentrations. We show that the low-energy Br-on-Cs antisite results in the formation of a polybromide (Br<sub>3</sub>) species that can exist in a range of charge states. We further demonstrate from excited-state calculations that tribromide moieties are photoresponsive and can contribute to the observed green luminescence. Photoactivity of polyhalide molecules is expected to be present in other halide perovskite-related compounds where they can influence light absorption and emission. <br>

The Coordination Chemistry of Phosphoryl Compounds Containing the — N(CH3)2 Group, Part VIII

1972 ◽  
Vol 27 (7) ◽  
pp. 759-763 ◽  
Author(s):  
M. W. G. De Bolster ◽  
W. L. Groeneveld
Keyword(s):  
Coordination Chemistry ◽  
General Formula ◽  
Ligand Field ◽  
Chemical Analyses ◽  
X Ray ◽  
Physical Measurements ◽  
Ligand Field Spectra ◽  
Chloride Adduct ◽  
Ligand Field Parameters ◽  
Group Part

A number of new solvates and adducts containing bisphenyldimethylaminophosphine oxide is reported. The solvates have the general formula M[(C6H5)2P(O)N(CH3)2]42+(anion-)2, in which M = Mg, Ca, Mn, Fe, Co, Ni, Cu, Zn and Cd, and the anions are ClO4- and BF4-. The adducts have the general formula M[(C6H5)2P(O)N(CH3)2]2Cl2, where M stands for the same series of metals.The compounds are characterized and identified by chemical analyses and physical measurements.Ligand-field and vibrational spectra have been investigated; values for the ligand-field parameters are reported. It is concluded that coordination takes place via the oxygen atom of the ligand.X-ray powder patterns were used in combination with ligand-field spectra to deduce the coordination around the metal ions.The interesting behaviour of the nickel (II) chloride adduct upon heating is discussed and it is shown that both a square pyramidal and a tetrahedral modification exists.

scholarly journals 3D Metal–Organic Frameworks Based on Co(II) and Bithiophendicarboxylate: Synthesis, Crystal Structures, Gas Adsorption, and Magnetic Properties

Molecules ◽  
2021 ◽  
Vol 26 (5) ◽  
pp. 1269
Author(s):  
Vadim A. Dubskikh ◽  
Anna A. Lysova ◽  
Denis G. Samsonenko ◽  
Alexander N. Lavrov ◽  
Konstantin A. Kovalenko ◽  
...  
Keyword(s):  
Room Temperature ◽  
Gas Adsorption ◽  
Magnetic Moments ◽  
Bet Surface Area ◽  
Separation Performance ◽  
Bridging Ligands ◽  
Magnetization Data ◽  
Metal Organic ◽  
Ch4 Adsorption ◽  
Gas Separation Performance

Three new 3D metal-organic porous frameworks based on Co(II) and 2,2′-bithiophen-5,5′-dicarboxylate (btdc2−) [Co3(btdc)3(bpy)2]·4DMF, 1; [Co3(btdc)3(pz)(dmf)2]·4DMF·1.5H2O, 2; [Co3(btdc)3(dmf)4]∙2DMF∙2H2O, 3 (bpy = 2,2′-bipyridyl, pz = pyrazine, dmf = N,N-dimethylformamide) were synthesized and structurally characterized. All compounds share the same trinuclear carboxylate building units {Co3(RCOO)6}, connected either by btdc2– ligands (1, 3) or by both btdc2– and pz bridging ligands (2). The permanent porosity of 1 was confirmed by N2, O2, CO, CO2, CH4 adsorption measurements at various temperatures (77 K, 273 K, 298 K), resulted in BET surface area 667 m2⋅g−1 and promising gas separation performance with selectivity factors up to 35.7 for CO2/N2, 45.4 for CO2/O2, 20.8 for CO2/CO, and 4.8 for CO2/CH4. The molar magnetic susceptibilities χp(T) were measured for 1 and 2 in the temperature range 1.77–330 K at magnetic fields up to 10 kOe. The room-temperature values of the effective magnetic moments for compounds 1 and 2 are μeff (300 K) ≈ 4.93 μB. The obtained results confirm the mainly paramagnetic nature of both compounds with some antiferromagnetic interactions at low-temperatures T < 20 K in 2 between the Co(II) cations separated by short pz linkers. Similar conclusions were also derived from the field-depending magnetization data of 1 and 2.

scholarly journals Absorption and Emission Spectra for C60 Anions

1994 ◽  
Vol 14 (1-3) ◽  
pp. 155-160 ◽  
Author(s):  
Tatsuhisa Kato
Keyword(s):  
Absorption Spectrum ◽  
Absorption Band ◽  
Theoretical Analysis ◽  
Room Temperature ◽  
Emission Spectra ◽  
Mirror Image ◽  
Ir Absorption ◽  
Near Ir ◽  
Laser Experiments ◽  
Ir Bands

Absorption spectra are detected for C60− and C602− produced electrolytically in solution at room temperature. Theoretical analysis of the spectrum of C60− by CNDO/S calculations gives an interpretation of the characteristic near-IR bands, the weak visible bands, and the strong bands in the UV region. The emission spectrum of C60− is a mirror image of the near-IR absorption band, and the detection of the emission reconfirms our original assignment of the absorption spectrum. The nature of the spectrum of C602− is characterized by a similar orbital picture to that of C60−. Further laser experiments of significance are proposed.

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