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991.
Single crystals of [CuCl0.85Br0.15(C6H4N3CH2=CH2)] (I) were obtained by alternating current electrochemical synthesis; their X-ray structural investigation has been carried
out (DARCh automatic diffractometer, MoK
α radiation, θ/2θ scanning; 1460 reflections with F ≥ 4σ(F), R = 0.0517). The crystals are monoclinic, their space group is P21/c, a = 7.292(3) Å, b = 17.947(8) Å, c = 7.398(4) Å, β = 93.56(4)°, V = 966(1) Å3, Z = 4). Complex I is close in structure to the previously investigated compound [CuCl(C6H4N3CH2=CH2)] (II). In both structures, the trigonal-pyramidal surroundings of the copper atom include two halide atoms (one is apical),
a nitrogen atom, and a C=C group. The Cu2X2 dimers are associated into {[Cu2X2(C6H5N3CH2=CH2)]}n layers due to the bridging function of the 1-allylbenzotriazole molecule. In spite of the similar coordination polyhedra
of the metal atoms and identical bridging function of the ligand molecule in I and II, the differences in the conformation
parameters of the allyl group π-coordinated by the copper(I) atom (trans-like in I and cis-like in II) caused by the presence
of bromine atoms in the coordination sphere predetermine different structures of the organometallic [Cu2X2(C6H5N3CH2=CH2)]4 tetramer subunits in the layers and, as a consequence, formation of different crystal structures.
Original Russian Text Copyright ? 2005 by E. A. Goreshnik, B. M. Mykhalichko, and V. N. Davydov
__________
Translated from Zhurnal Strukturnoi Khimii, Vol. 46, No. 1, pp. 174–178, January–February, 2005. 相似文献
992.
A. D. Dubonosov V. P. Rybalkin Ya. Yu. Vorob’eva V. A. Bren’ V. I. Minkin S. M. Aldoshin V. V. Tkachev A. V. Tsukanov 《Russian Chemical Bulletin》2004,53(10):2248-2252
It was shown by electron absorption spectroscopy and X-ray diffraction analysis that steric strains in photochromic 2-(N-acyl-N-arylaminomethylene) benzo[b]thiophen-3(2H)-one molecules ortho-substituted in the N-phenyl ring increase the quantum yield of the N→O photoinduced rearrangement in accord with an increase in the steric constant of the ortho-substituent.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 2151–2155, October, 2004. 相似文献
993.
Tomislav P. Živković 《Journal of mathematical chemistry》2002,32(1):39-71
Interaction of quantum system S
a
described by the generalised × eigenvalue equation A|
s
=E
s
S
a
|
s
(s=1,...,) with quantum system S
b
described by the generalised n×n eigenvalue equation B|
i
=
i
S
b
|
i
(i=1,...,n) is considered. With the system S
a
is associated -dimensional space X
a
and with the system S
b
is associated an n-dimensional space X
n
b
that is orthogonal to X
a
. Combined system S is described by the generalised (+n)×(+n) eigenvalue equation [A+B+V]|
k
=
k
[S
a
+S
b
+P]|
k
(k=1,...,n+) where operators V and P represent interaction between those two systems. All operators are Hermitian, while operators S
a
,S
b
and S=S
a
+S
b
+P are, in addition, positive definite. It is shown that each eigenvalue
k
i
of the combined system is the eigenvalue of the × eigenvalue equation
. Operator
in this equation is expressed in terms of the eigenvalues
i
of the system S
b
and in terms of matrix elements
s
|V|
i
and
s
|P|
i
where vectors |
s
form a base in X
a
. Eigenstate |
k
a
of this equation is the projection of the eigenstate |
k
of the combined system on the space X
a
. Projection |
k
b
of |
k
on the space X
n
b
is given by |
k
b
=(
k
S
b
–B)–1(V–
k
P})|
k
a
where (
k
S
b
–B)–1 is inverse of (
k
S
b
–B) in X
n
b
. Hence, if the solution to the system S
b
is known, one can obtain all eigenvalues
k
i
} and all the corresponding eigenstates |
k
of the combined system as a solution of the above × eigenvalue equation that refers to the system S
a
alone. Slightly more complicated expressions are obtained for the eigenvalues
k
i
} and the corresponding eigenstates, provided such eigenvalues and eigenstates exist. 相似文献
994.
Norman O. Smith 《Journal of solution chemistry》1994,23(4):521-539
A method of finding the activity coefficients of salts, anhydrous or hydrated, in binary solid solutions, described in an earlier paper as it applies to continuous series, has been applied to discontinuous series. The salts must differ with respect to only one ion. The method requires isothermal distribution data for equilibria between liquid (aqueous) and solid solutions in the ternary system consisting of the two salts and water. The following salt pairs were used for illustration: K(I/Br) at 0, 15, 25, 35, and 50°C., (NH4/K)SCN at 0, 30, 60, and 90°C., (K/Tl)C103 at 10°C., and (NH4/K)SO3NH2, (NH4/K)Br, (Mg/Co)SO4-7H2O, and (Mn/Cu) SO4.n H2O-all at 25°C. Two kinds of behavior were noted and treated differently: systems in which the two series have the same, and those in which they have different crystal lattices. For two salts, A and B, which have the same lattice, and whose rational activity coefficients, f
A
and f
B
, can be described by 2-suffix Margules equations (regular solutions), lnf
A
=Bsx
B
2
and lnf
B
=Bsx
A
2
to be partially miscible, Bs>2, but this requirement does not apply if the lattices are different. In each series, distribution constants for the equilibria were also determined. Where possible, the calculated activities of the salts or the Gibbs excess energies of the solid solutions were compared with values reported by others who determined them by other methods. All the salt pairs studied show slight or strong positive deviations from ideality. 相似文献
995.
The molecular structure and absorption spectra of monothio- and dithio-naphthalimides were compared to their naphthalimide analogues using AM1, PM3 and ZINDO/S semiempirical quantum chemical methods. The substitution of the 4R-naphthalimide oxygen atoms by sulphur atoms resulted in a red-shift of the absorption spectra by Δλmax60-65 and 100-140 nm, respectively. The thionated naphthalimide derivatives do not show observable fluorescence due to intersystem crossing to the triplet -states localised at the CS groups. The -absorption bands of monothioimides are located at 525-580 nm (ε=60-80) and those for dithioimides at 535-560 nm (ε=140-390) and 628-686 nm (ε=34-68). None of these transitions are solvent sensitive. The -transitions of N-phenylthioimides have also a small contribution from -states due to a partial conjugation between CS group and π-electronic system of the N-phenyl ring. As a result, the bands of aromatic substituted N-phenylthioimides are red-shifted as compared to those of the aliphatic N-methyl-thioimides. 相似文献
996.
Michael Chariss Andrea Zickgraf Heike Stenger Elmar Bru Cristelle Desmarquet Martin Drger Silke Gerstmann Dainis Dakternieks James Hook 《Polyhedron》1998,17(25-26)
44 members of thecompound series Ph4−nMRn (M=Si, Ge, Sn, Pb; R=o-, m-, p-Tol; n=0–4) were synthesized (15 newcompounds). The crystal structures of Ph3Sn (o-Tol) and PhSn (o-Tol)3 were determined and compared to 16 known structures. Subject to the distanced (M–C), an interplay between through-space π–π repulsion and π–σ attraction leads to either elongated or compressed tetrahedral geometry. 29 Si-, 119 Sn- and 207 Pb-NMR chemical shifts were determined in solution and in the solid state. 73 Ge chemical shifts were measured only in solution. Anupfield or downfield sagging of the chemical shifts along each series is rationalized in terms of a π–σcharge transfer which is constrained by torsion of the aromatic groups. 相似文献
997.
The development of novel microanalytical techniques forin situ chemical characterization of the terrestrial subsurface environment has grown significantly over the last decade, particularly those instruments that are interfaced to the cone penetrometer. Cone penetrometer testing (CPT) has emerged as an effective means to introduce samplers and probes forin situ analysis of contaminants in soil and groundwater matrices. A variety ofin situ chemical samplers for CPT have been developed that can be driven into the subsurface to collect soil gas, groundwater, or soil samples at depth, thus providing a means of determining the vertical and horizontal extent of contamination. Cone penetrometer testing is also being explored as a means to deliverin situ subsurface sensor probes, including probes based on laser-induced fluorescence, Raman, and infrared spectroscopies for organics; on laser-induced breakdown and X-ray fluorescence spectroscopies for heavy metals; and on passive gamma-ray spectroscopy for radionuclides. The range of analytical technologies used in CPT for the determination of organic and inorganic species in the subsurface is described. 相似文献
998.
T. V. Magdesieva A. V. Dolganov P. M. Polestchuk A. V. Yakimanskii M. Ya. Goikhman I. V. Podeshvo V. V. Kudryavtsev 《Russian Chemical Bulletin》2007,56(7):1380-1389
Structural reorganization of polyamide (PA) and low-molecular-weight CuI and CuII complexes with biquinolyl (biQ) ligands during their mutual redox transformations in solution was studied using the electrochemical
methods (cyclic voltammetry and preparative electrolysis) and quantum chemical DFT calculations. The influence of electronic
factors and geometry distortions in the complexes on the ionization energy on going from CuI to CuII was evaluated in comparison. The catalytically active form of the [CuI(PA)L2]BF4 complex can be synthesized in situ from the stable tetrahedral complex [CuI(PA)2]BF4 by the series of successive redox transitions CuI → CuII → CuI accompanied by the loss of one biQ-containing macroligand.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1331–1340, July, 2007. 相似文献
999.
Michael C. Bhm Joachim Schulte Rafael Ramírez 《International journal of quantum chemistry》2002,86(3):280-296
The absolute magnetic shieldings of benzene and ethylene have been theoretically studied under the conditions of thermal equilibrium, i.e., under explicit consideration of the nuclear degrees of freedom. For this purpose we have combined the Feynman path integral quantum Monte Carlo (PIMC) formalism with the gauge‐including atomic orbital (GIAO) approach in the Hartree–Fock (HF) approximation. The HF operator has been employed to derive the NMR parameters of the two hydrocarbons via an ensemble averaging over large sets of molecular configurations that are populated in thermal equilibrium. The nuclear fluctuations are responsible for a deshielding of the nuclei relative to the shieldings at the vibrationless minimum of the potential energy surface (PES). The influence of the nuclear degrees of freedom is largest for the isotropic part of the 13C shielding tensor. The theoretical results can be explained on the basis of simple geometrical considerations. The bond lengths in thermal equilibrium are larger than the bond lengths at the minimum of the PES. This length enhancement is the prerequisite for a deshielding of the nuclei in thermal equilibrium. The vibrational corrections of the nuclear magnetic resonance (NMR) parameters of benzene and ethylene are quantum driven; classical thermal degrees of freedom of the nuclei are of minor importance. Conceptual problems of theoretical studies of NMR parameters on the basis of a single molecular geometry are emphasized. The influence of the spatial uncertainty of the nuclei becomes decisive in molecules with light atoms. It is pointed out that the combination of the PIMC formalism with electronic Hamiltonians of state‐of‐the‐art quality renders possible accurate determinations of NMR parameters. © 2002 John Wiley & Sons, Inc. Int J Quantum Chem 86: 280–296, 2002 相似文献
1000.
The 57Fe Mössbauer effect in [Fe(pythiaz)2] (BF4)2 (I) and [Fe(pythiaz)2] (C&O4)2 (II) has been studied between 298 and 4.2°K (pythiaz = 2,4-bis(2-pyridyl)thiazole). At 298°K compound I shows a doublet with ΔEQ(5T2) = 1.29 mm sec?1 and δ1S(5T2) = +0.93 mm sec?1 characteristic of a 5T2 ground state. At 236°K, a second doublet, typical for a 1A1 ground state appears. The transition 5T2 å 1A1 progresses as the temperature is lowered but levels off below ≈ 120°K. At 4.2°K, 59% of the intensity is due to the 1A1 state, and ΔEQ(1A1) = 1.59 mm sec?1 and δ1S(1A1) = +0.26 mm sec?1. In an applied magnetic field, Vzz(1A1) < 0 has been determined Similar results have been obtained with compound II.Debye-Waller factors f5T2 and f1A1. were determined from the Mössbauer spectra under the assumption of Curie-Weiss dependence of the magnetism for the 5T2 and constant μeff for the 1A1 ground state. The resulting temperature dependence of f1A1 is highly unusual thus suggesting complicated magnetic behaviour of both ground states in the transition region. Two mechanisms for the nature of the transition are discussed, a “spin-flip” mechanism being the physically more reasonable one. The assumption of a simple Boltzmann distribution (“spin equilibrium”) may be ruled out for the solid but could be encountered in solutions. 相似文献