Lanthanide SMMs Based on Belt Macrocycles: Recent Advances and General Trends

Enhancement of axial magnetic anisotropy is the central objective to push forward the performance of Single-Molecule Magnet (SMM) complexes. In the case of mononuclear lanthanide complexes, the chemical environment around the paramagnetic ion must be tuned to place strongly interacting ligands along either the axial positions or the equatorial plane, depending on the oblate or prolate preference of the selected lanthanide. One classical strategy to achieve a precise chemical environment for a metal centre is using highly structured, chelating ligands. A natural approach for axial-equatorial control is the employment of macrocycles acting in a belt conformation, providing the equatorial coordination environment, and leaving room for axial ligands. In this review, we present a survey of SMMs based on the macrocycle belt motif. Literature systems are divided in three families (crown ether, Schiff-base and metallacrown) and their general properties in terms of structural stability and SMM performance are briefly discussed.     

Dispersion of waves in a plane acoustic layer with flexible elastic walls

A plane acoustic layer bounded by elastic membranes is considered. Dispersion relations for symmetric and antisymmetric waves are derived. The limit behavior of dispersion curves is investigated for wave numbers tending to zero and to infinity. With the use of the resulting asymptotic expansions, the two-point Pade approximations are constructed. The orthogonality relations for eigenmodes are presented.     

Methods of constructing optimal stabilizers

The problem of transforming a linear dynamical system in the neighbourhood of a state of equilibrium [1,2] is solved using the special problem of the damping of the system by controls of minimum intensity after a finite time interval. The possibility of using other problems of optimal control is discussed. The main attention is devoted to constructing algorithms of the operation of a device (a stabilizer) which is able, in real time, to generate a stabilizing control circulating in the closed optimal system when unknown perturbations operate constantly [3, 4]. The proposed method is based on the constructive theory of optimal control [5, 6]. Another form of this theory for solving the problem of stabilization is presented in [7](see also [8]).     

Method for determining the first excited “hole” state in radicals

A technique is presented for determining th eexcited hole state in radicals using the approximation of an (N – 3)-electron, quenched molecular shell. Results are given on the equilibrium geometry and the transition energies in emission and absorption for the radicals SiH, CH, CN, NH₂, and PH₂ with the CNDO approximation. The equilibrium geometry of the radicals in the excited state corresponds well with the experimental results. A qualitative correlation for the calculated and experimental values of the transition energies is obtained.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 65–69, July, 1986.     

The crystal and molecular structure of cesium 9,10,11-trimethyl-7,8-dicarba-nido-undecaborate(1-) Cs[9,10,11-Me3-7,8-C2B9H9]

Conclusions By a complete x-ray diffraction study of cesium 9,10,11-trimethyl-7,8-dicarba-nido-undecaborate(1-) we proved the axial orientation of the Me group attached to the B¹⁰ atom of the open face of the nido-carborane polyhedron. This serves as an additional proof of the stereospecificity of the alkylation reaction of the dicarbollide ions and the necessity for a migration stage of the boron atom with the substituent to the site of the deficient apex of the icosahedron to form a derivative with an equatorial disposition of the alkyl group.The atoms in the carborane polyhedron are numbered as in [1].Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2474–2481, November, 1979.     

Cis‐trans Isomerism in Copper(II) Complexes with N‐acyl Thiourea Ligands

The N‐acyl thiourea complexes bis[N,N‐diethyl‐N′‐(p‐nitrobenzoyl)‐thioureato]copper(II) ( 1a,1b ) and bis(N,N‐diphenyl‐N′‐benzoylthioureato)copper(II) ( 2a,2b ) crystallize in each case in two modifications. X‐ray structural analysis shows that 1a and 1b are cis‐trans isomers. This is very unusual for N‐acyl thioureato complexes because with exception of one platinum(II) complex up to now only cis complexes have been found. In contrast X‐ray structural analysis of both forms 2a and 2b of the other complex shows no cis‐trans pair. Both modifications are cis complexes. In solution both isomers of the copper(II) complexes are observable by EPR spectroscopy.     

Chemistry of heteroanalogs of isoflavones

Condensation of 2-pyridylacetonitrile with polyphenols gave the corresponding -(2-pyridyl)-acetophenones, which were converted to the pyridine analogs of natural isoflavones and to 3-pyridylchromones with methyl, trifluoromethyl, and ethoxycarbonyl groups in the 2 position. The antimicrobial activity of 3-pyridylchromones and their reaction with alkylating and acylating agents and phosphorus pentasulfide were investigated.See [1] for communication V.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1180–1185, September, 1977.     

Porphyrins. 33. Proton magnetic resonance spectra of hematoporphyrin derivatives. properties of a dimethoxy derivative (dimegin) in aqueous solution

The PMR spectra of derivatives of hematoporphyrin IX have been investigated in organic and aqueous solution. It has been shown that the presence of the two chiral centers at positions 2 and 4 of the macrocycle is displayed in the specific splitting of the signals of the meso protons. The structures of dimeric associates of 2,4-di(-methoxyethyl)-deuteroporphyrin IX (dirnegin) have been studied in aqueous solution over a wide pH range and have the structure of a skewed sandwich according to PMR data.For Communication 32, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 198–204, February, 1996.