Estimation of Photoelectrocatalytic Activity of Titanium Oxide Film Electrodes by Ac Impedance

Over the last few decades, there has been a growing interest in the application of photocatalysis towards the treatment of polluted water1-4. It was well demonstrated that the anodic bias potential exerted on photoanode could prevent significantly the recombination rate of photogenerated carriers, consequently, it can improve the efficiency of photocatalytic degradation of organics2-4. For this, the study of photoelectrocatalytic degradation of pollutants has been of particular interest to r…     

Probing the Electrostatic Barrier of Tetrathiafulvalene Dications using a Tetra-stable Donor–Acceptor [2]Rotaxane

A tetra-stable donor–acceptor [2]rotaxane 1 ⋅4PF₆ has been synthesized. The dumbbell component is comprised of an oxyphenylene (OP), a tetrathiafulvalene (TTF), a monopyrrolo-TTF (MPTTF), and a hydroquinone (HQ) unit, which can act as recognition sites (stations) for the tetra-cationic cyclophane cyclobis(paraquat-p-phenylene) (CBPQT⁴⁺). The TTF and the MPTTF stations are located in the middle of the dumbbell component and are connected by a triethylene glycol (TEG) chain in such a way that the pyrrole moiety of the MPTTF station points toward the TTF station, while the TTF and MPTTF stations are flanked by the OP and HQ stations on their left hand side and right hand side, respectively. The [2]rotaxane was characterized in solution by ¹H NMR spectroscopy and cyclic voltammetry. The spectroscopic data revealed that the majority (77 %) of the tetra-stable [2]rotaxane 1 ⁴⁺ exist as the translational isomer 1 ⋅MPTTF⁴⁺ in which the CBPQT⁴⁺ ring encircles the MPTTF station. The electrochemical studies showed that CBPQT⁴⁺ in 1 ⋅MPTTF⁴⁺ undergoes ring translation as result of electrostatic repulsion from the oxidized MPTTF unit. Following tetra-oxidation of 1 ⋅MPTTF⁴⁺, a high-energy state of 1 ⁸⁺ was obtained (i.e., 1 ⋅TEG⁸⁺) in which the CBPQT⁴⁺ ring was located on the TEG linker connecting the di-oxidized TTF²⁺ and MPTTF²⁺ units. ¹H NMR spectroscopy carried out in CD₃CN at 298 K on a chemically oxidized sample of 1 ⋅MPTTF⁴⁺ revealed that the metastable state 1 ⋅TEG⁸⁺ is only short-lived with a lifetime of a few minutes and it was found that 70 % of the positively charged CBPQT⁴⁺ ring moved from 1 ⋅TEG⁸⁺ to the HQ station, while 30 % moved to the much weaker OP station. These results clearly demonstrate that the CBPQT⁴⁺ ring can cross both an MPTTF²⁺ and a TTF²⁺ electrostatic barrier and that the free energy of activation required to cross MPTTF²⁺ is ca. 0.5 kcal mol⁻¹ smaller as compared to TTF²⁺.     

Polymorphism of Supramolecular Charge-Transfer Complex Composed of 10,10′-dihydroxy-9,9′-biphenanthryl and p-benzoquinone

Charge-transfer (CT) complexes were prepared using racemic (rac)-10,10′-dihydroxy-9,9′-biphenanthryl, which has a large and highly π-conjugated phenanthrene ring, as the electron donor and p-benzoquinone as the electron acceptor. This CT system showed a polymorphism.     

Enhanced Photostability and Red-NIR Photosensitivity of Conjugated Polymer Charge-Transfer Complexes

A promising route to photostable and low-bandgap polymer materials for optoelectronic and photonic applications could be utilization of donor-acceptor ground-state charge-transfer complexes (CTCs) of wide-bandgap conjugated polymers. In this work, we report our results on photostability and photoelectric studies of CTC between an archetypical conjugated polymer MEH-PPV and low-molecular-weight acceptor 2,4,7-trinitrofluorenone (TNF). By using the pump-probe laser photobleaching technique, we show that the photodegradation rate of MEH-PPV:TNF blend films decreases up to four orders of magnitude as compared with pristine MEH-PPV. By using photocurrent and surface photovoltage spectroscopies, we demonstrate that the photoelectric sensitivity of the MEH-PPV:TNF CTC can be deeply extended in the polymer optical gap down to 1 µm. However, the main drawback of the CTC studied is their low charge collection efficiency, and an approach to increasing it is discussed.     

Photoredox Chemistry of Polyoxometalates as a Photocatalyst

The photocatalytic action of polyoxometalates (PMs), which is initiated by the photoexcitation of the oxygen-to-metal charge-transfer (O M LMCT) bands of PM, is based on the electron–hole pair separation followed by reductive and oxidative reactions with surrounding molecules. It is shown that the O M LMCT triplet states are involved in the photoredox reactions in which the significance of the highly negative oxidation potential for the photoreduced PMs can be considered in connection with the photocatalytic H₂ formation from a great variety of organic substrates with their dehydrated oxidation. When the reaction of the photoreduced PMs with the electron acceptor hardly occurs kinetically or thermodynamically, they undergo self-assembled organization to nanosized supramolecules (as a result of photoencapsulation of small molecules and ring cluster formation). Some typical examples for the electron–hole pair separation and the photoredox reactions developed in our laboratory are discussed.     

Solvent effects in molecular complexes of porphyrins and metalloporphyrins

The apparent stability constants for porphyrin and metalloporphyrin complexes with an electron acceptor have been determined in mixed solvents. The variation of the apparent stability with solvent composition is evaluated in terms of solvation of the complex and reactant species and in terms of the exclusion of the solvent from the solvation sheath of the reactants, according to the equilibrium AS _a +DS _b =CS _x +yS.     

31P CP-MAS NMR,Vibrational, and X-Ray Characterization of the Adducts of Triphenylphosphine Sulfide with ICl and IBr

The reactions between triphenylphosphine sulfide (Ph₃PS) and ICl in CCl₄ and IBr in CH₂Cl₂ in 1 : 1 molar ratio give the solid adducts Ph₃PS · ICl ( I ) and Ph₃PS · IBr ( II ) whose structures have been solved by X-ray diffraction. Compounds I and II consist of discrete molecule units and feature the S–I–Cl or S–I–Br linear group. The S–I bond distances in I , II (2.641(1), 2.665(1) Å respectively) and in compound 2 Ph₃PS · 3 I₂ ( III ) (2.729(2) Å) are correlable to the net increase in the I–X (X = Cl, Br, I) bond distance. The structural features of I , II and III are in accordance with ³¹P CP–MAS NMR, FT-Raman and FT-IR spectral data, and elucidate the nature of the donor (Ph₃PS)-acceptor (ICl, IBr, I₂) interaction.     

新型电荷转移配合物的合成与表征

近年来有关多金属氧酸盐与有机化合物间电荷转移配合物的光化学和光致变色过程的研究日趋活跃［１,２］,但迄今这类电荷转移配合物中的多金属氧酸盐基本上为Ｌｉｎｄｑｕｉｓｔ结构的同多酸或Ｋｅｇｇｉｎ结构的杂多酸,有机给体则基本上限于有机胺及其衍生物（如酰胺）...     

Theoretical Studies of Electron Paramagnetic Resonance Parameters for Cr4+ Ions in Ca2GeO4 Crystals

The electron paramagnetic resonance (EPR) parameters (zero-field splitting D and g factors g_||, g_⊥) of Cr⁴⁺ ions in Ca₂GeO₄ crystals have been calculated from the complete high-order perturbation formulas of EPR parameters for a 3d² ion in trigonal MX₄ clusters. In these formulas, in addition to the contributions to EPR parameters from the widely used crystal-field (CF) mechanism, the contributions from the charge-transfer (CT) mechanism (which are often neglected) are included. From the calculations, it is found that for the high valence state 3dⁿ ions in crystals, the reasonable explanation of EPR parameters (in particular, the g factors) should take both the CF and CT mechanisms into account.     

六次甲基四胺与HnXW12O40．mH2O(X=P,Si,Ge)电荷转移盐的合成、表征及非线性光学性质研究

合成了由六次甲基四胺与H