Novel Properties of Supramolecular Complexes Formed by Pairing Cationic Porphyrin and Anionic Metal-Oxo Cluster

MTBPyP (meso-tetrakis(4-N-benzylpyridyl)porphyrin, M=H-2, Zn) bearing positive charge has been shown to associate with SiW12O404- in water solution. The spectral evolution and Job's plots analyses reveal that the relatively stable aggregates contain equal numbers of MTBPyP4(+) and SiW12O404-.

Theoretical Investigations of Nonlinear Optical Properties of Transition Metal Cluster Anions

In the framework of density functional theory （DFT）, the electronic excitations and nonlinear optical （NLO） properties of six binuclear transition metal cluster anions with the formula of [Ch2M-（μ-Ch）2-M＇CN]^2- （M = Mo, W; Ch = S, Se; M＇ = Cu, Ag） have been systemically investigated at both cases of gas phase and DMF solution. The obtained electronic absorption spectra reveal that the element replacements of metals M and ligands Ch have significant influence on the absorptions, especially on the low-lying ones. In addition, the transitions of μ-Ch→M are dominant for the low-lying excitations, whereas the transitions of M＇→M as well as Ch→M are mainly responsible for the higher excitations. The calculated molecular first and second hyperpolarizabilities present the remarkable element substitution and solvent effects. The analyses show that the transitions involving μ-Ch→M charge transfer make the critical contributions to the first hyperpolarizability t, and that the charge transfers from the moieties of MCh4 to M＇CN as well as those of μ-Ch→M and M＇→M are responsible for the second hyperpolarizability y. Moreover, the introduction of solvent leads to the results that the transitions within the moieties of MCh4 and M＇CN make larger contributions to the hyperpolarizability, especially to γ.

Novel Lanthanide Cluster Polymers Based on Cubane-like [Ln4(OH)4]^8＋ Clusters and Sulfate Anions

Two lanthanide-oxo-cluster polymers were synthesized by hydrothermal reaction using Ln_2O_3 as initial lanthanide materials：[Ln_4（SO_4）_4（OH）_4（H_2O）_7]·_4H_2O（Ln = Er 1,Ho 2）,and characterized by PXRD,IR spectra,X-ray single-crystal diffraction,2D IR correlation spectra and UV-visible absorption spectra.Single-crystal X-ray analyses reveal that compounds 1 and 2 are isostructural,and they are both crystallized in the orthorhombic system Pccn space group.Compound 1 is a 3D lanthanide cluster polymer based on tetranuclear cubane-like [Er_4（μ_3-OH）_4]^8＋ cations and SO_4^2- anions.The overall structure of 1 can be assigned to 6-connected pcu-type topology with the point symbol of（4^12.6^3）.

The hyperfine structure of electron spin resonance spectrum of tricobalt cluster radical anion CH_3CCo_3(CO)_9^-

CH_3CCo_3(CO)_9 was synthesized from the reaction between chloralose and Co_2(CO)_. The radical anion was generated by electrochemical reduction,and electron spin resonance spectra in THF were recorded by in situ electrolysis in the sample tube in the ESR cavity at 298 and 110K with the spectral data