酞菁（H_2TAP）的X－射线光电子能谱（XPS）

酞菁（Ｈ_２ＴＡＰ）的Ｘ－射线光电子能谱（ＸＰＳ）朱志昂，卜显和，刘月霞（南开大学化学系天津３０００７１）ＰａｕｌＧ．Ｇａｓｓｍａｎ（美国明尼苏达大学化学系）关键词酞青，ＸＰＳ，Ｃ１ｓ电子结合能，Ｎ１ｓ电子结合能酞菁及其金属配合物作为叶绿素，血红素的?..     

Vibrational Spectra and Density Functional Theory Calculations of Metallo-tetra-(tert-butyl)-tetra-azaporphyrines

The infrared absorption and 514.5 nm excited Raman spectra were measured for the metallo-tetra-(tert-butyl)-tetraazaporphyrin (MT(tBu)TAP, M=Cu, Co, Ni, Zn). The ground-state structures and vibrational spectra of MT(tBu)TAPs have been calculated at the B3LYP level of theory. The observed Raman and IR bands have been assigned based on the calculation results and by comparing with the normal metalloporphyrins. The relationship between the Raman/IR frequencies and the structures of TAP ring was investigated. The results show that the frequencies of C_βC_β′ stretch (A_g), asymmetric C_αN_m stretch (A_g), and symmetric C_αN_m stretch (B_g) modes increase linearly with the decrease of the core-sizes of TAP ring.Among the three modes, the later two are more sensitive to the core-size change.     

四-(叔丁基)-四氮杂卟啉金属配合物的振动光谱和DFT计算

测量了四-(叔丁基)-四氮杂卟啉金属配合物(MT(tBu)TAP,M=Cu, Co, Ni, Zn)的拉曼和红外光谱. 在B3LYP理论水平上计算了其基态结构和振动光谱,基于计算结果对观察到的拉曼谱带进行了详细的指认. 考察了拉曼和红外谱带频率变化与四氮杂卟啉环结构的关系. 随着环内核尺寸的减小,C_βC_β′伸缩振动(A_g)、C_αN_m反对称伸缩振动(A_g)、以及C_αN_m对称伸缩振动(B_g) 的频率线性地增加,其中后两者对环内核尺寸的变化更为敏感.     

Metallo-tetraazaporphyrin based anion sensors: regulation of sensor characteristics through central metal ion coordination

The iron(III) and cobalt(III) complexes of 2,3,7,8,12,13,17,18-octakis(benzylthio)-5,10,15,20-tetraazaporphyrin, (OBTAP) were synthesized and incorporated into PVC matrix as ionophores to fabricate anion selective membrane electrodes that exhibit selective potentiometric response to azide and nitrite ions, respectively. The membrane of [Fe(OBTAP)]⁺ (III) with a composition of 6:190:200 (III:DBP:PVC) (w/w), and of [Co(OBTAP)]⁺ (IV) with a composition of 10:148:200 (IV:DOP:PVC) (w/w), i.e. 1a and 2b, respectively (where DBP:dibutylphthalate and DOP=dioctylphthalate) gave the best performance. The membrane 1a showed a slope of 29.2±0.2 mV per decade of activity for N₃⁻ in the working concentration range of 8.9×10⁻⁶ to 1.0×10⁻¹ M. The membrane 2b showed a slope of 30.0±0.2 mV per decade of activity for NO₂⁻ in the working concentration range of 1.1×10⁻⁵ to 1.0×10⁻¹ M. The membranes worked satisfactorily in the pH range of 4.3-10.5 (1a) and 2.8-6.4 (2b) and had fast response time of 12±2 and 13±2 s, respectively. Electrodes exhibited a high degree of selectivity for N₃⁻ and NO₂⁻, respectively, over several other monovalent and bivalent anions. Only SCN⁻ and S²⁻ (at >1.0×10⁻⁴ M) cause moderate interference for electrode 1a and Cl⁻ and S²⁻ (at >1.0×10⁻⁵ M) for electrode 2b. They gave reproducible results with the relative standard deviation in the observed values of potentials (σ) of 1.96 and 1.80 mV for electrodes 1a and 2b, respectively, from the least-squares fit line. The 90% confidence limit lies within ±0.2 mV per decade of activity. Reproducible results were obtained over a period of 5 months. Their performance in non-aqueous solvent mixtures having up to 50% (v/v) methanol, ethanol and acetone were evaluated and were found satisfactory. The proposed sensors are superior in terms of detection limit and response time in comparison to the reported ones.     

Dimers, trimers and oligomers of phthalocyanines and related compounds

Cofacial and planar homo- and heteroleptic dimers and oligomers of phthalocyanine (Pc) and its analogues reported to date have been reviewed.     

Syntheses,Spectral and Electrochemical Investigation of Coordination Complexes of Octakis(benzylthio)tetraazaporphyrinmaganese(II)

Synthesis of [Mn(OBTTAP)], 1 and bichromophoric, di- and pentanuclear complexes with diimine-ruthenium(II) of the type [{Mn(OBTTAP)}{Ru(bpy)₂}][PF₆]₂, 2, [{Mn(OBTTAP)}{Ru(phen)₂}][PF₆]₂, 3, [{Mn(OBTTAP)}{RuCp(PPh₃)}][PF₆], 4, [{Mn(OBTTAP)}{Ru(bpy)₂}₄]- [PF₆]₈, 5, [{Mn(OBTTAP)}{Ru(phen)₂}₄][PF₆]₈, 6 and [{Mn(OBTTAP)}{RuCp(PPh₃)}₄][PF₆]₄, 7, (OBTTAP = octakis(benzylthio)tetraazaporphyrin) have been described. They were characterized using IR, ¹H NMR, UV–visible, and mass spectral data. In the electronic absorption spectra the relative intensities and positions of the Soret and Q-bands, in the di- and pentanuclear complexes were observed shifted vis-à-vis that in the precursor complex 1. They all exhibit strong S₂ emission. The emission intensity of the equimolar solutions of complexes 2, 3, 4 and 7 were found to be significantly higher than that of 1. The excitation-emission behaviors of the complexes are indicative of interchromophore energy transfer. Complexes 2–7 exhibited good electrode activity, particularly with multiple reversible redox waves in oxidative CV scans. The OBTTAP ring oxidations were observed as one or two reversible waves, depending upon number and nature of the peripheral metal units. Particularly, with four (bpy)₂Ru^II units bonded to the [Mn(OBTTAP)] periphery, it was observed as two reversible, one electron oxidation waves at E _1/2 0.81 and 1.02 V vs. Ag/AgCl. Also the Ru(II)/Ru(III) oxidations were observed at significantly lower potential, in this complex, at E_1/2 0.49 V vs Ag/AgCl due to weaker π-inteaction with dπ(S) orbitals.