Syntheses, Structures, and Electrochemical Properties of Metallacyclic Oxidovanadium(V) Complexes with Asymmetric Multidentate Linking Ligands.

Trinuclear metallacyclic oxidovanadium(V) complexes, [{VO(L3+2R)}3] (1-3) with asymmetric multidentate linking ligands (H3L3+2R: R = H, Me, Br), were synthesized. The molecular structure of 1 is characterized as a tripod structure, with each V(V) ion coordinated by ONO-atoms from a tridentate Schiff base site and ON-atoms from a bidentate benzoxazole site of two respective H3L3+2H ligands. The intramolecular V⋯V distances range from 8.0683 to 8.1791 Å. Complex 4 is a mononuclear dioxidovanadium(V) complex, (Et3NH)[VO2(HL3+2H)]. Cyclic voltammograms of 1-3 in DMF revealed redox couples attributed to three single-electron transfer processes.

Detailed magnetic analysis and successful deep-neural-network-based conformational prediction for [VO(dmso)5][BPh4]2.

Pentakis(dimethylsulfoxide-κO)oxidovanadium(iv) bis(tetraphenylborate), [VO(dmso)5][BPh4]2 (dmso: dimethylsulfoxide), was synthesized, and its pseudo-C 4 VO6 coordination geometry was revealed by a single-crystal X-ray method. A novel equation set was obtained for magnetic susceptibility and magnetization of the d1 complexes, considering the axial distortion and the spin-orbit coupling for the 2D free-ion term. The equation set enabled magnetic simulation for significantly symmetry-lowered d1 complexes to obtain the anisotropic g-values and also the excitation energies. In addition, conformational prediction was conducted, using the enumeration results on the basis of the group theory. The dominant conformers were predicted on the basis of the density functional theory (DFT) method, and especially, the conformer in the crystal was successfully predicted by a deep neural network method.

Magneto-structural correlation of hexakis-dmso cobalt(ii) complex.

The magnetostructural correlation of the hexakis-dmso cobalt(ii) complex, [Co(dmso)6](BPh4)2 (dmso: dimethylsulfoxide), was investigated by single-crystal X-ray diffraction study and magnetic measurements. The magnetic analysis concluded the negative Δ value (H = Δ(L - 2/3) + E(L - L) - (3/2)κλL·S + ß[-(3/2)κLu + geSu]·Hu (u = x, y, z)), and this was explained by the tetragonal elongation of the octahedral geometry. The magnetostructural correlation was ascertained by both the angular overlap model calculation and the density functional theory calculation.

Insertion of a strongly pi-pi stacked chloranilate pair into an M4 arrangement preorganized within a large macrocyclic ligand (M = Zn2+ and Cu2+).

Four Zn(II) ions arranged within a pyridine-modified large phenolate-containing macrocyle Lpy2- encapsulate two chloranilate ions in a double bis-didentate bridging fashion; the ligands are strongly pi-pi stacked with each other with a short distance of 3.27 A and are electrochemically reduced at the same potential of -1.00 V to produce a reasonably stable biradical species with T1/2 = 60 min at 25 degrees C.