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1.
Unsymmetrical porphyrazines bearing a single peripheral bis(hydroxyethylthio) moiety were synthesised by mixed condensation of bis(2-hydroxyethylthio)maleonitrile and phthalonitrile. Complexation of the thioether groups of metal-free porphyrazine with PdCl2 further lowered the intensity of the Q-band absorption of the porphyrazine core. The new compounds were characterised by elemental analyses, IR, 1H NMR, UV-Vis, and mass spectra. 相似文献
2.
Summary. In this study, the electrochemical properties of novel porphyrazines with eight crown ether substituents appending on the
periphery through flexible chains were investigated by using cyclic voltammetry and controlled potential coulometry. Cyclic
voltammetry measurements showed that the metal free porphyrazine gave all of the six possible redox reactions of common porphyrazine
derivatives. Cobalt porphyrazine exhibited a metal-based reduction and a metal-based oxidation processes followed by two ligand-based
reduction and two oxidation processes. I
p vs. ν1/2 plots of redox processes of the two compounds indicated the diffusional mass transfer mechanism of the complexes. Copper
porphyrazine gave an oxidation process having adsorption properties and three reduction reactions. The variations of peak
current ratios of electrochemical reactions for all three complexes with scan rate showed that electron transfer processes
of complexes were followed by reversible or irreversible chemical reactions. Aggregation and sandwich adduct formation properties
of complexes were determined by CV measurements. Peak potentials of redox processes for all complexes were shifted towards
positive potentials by addition of alkali metal cations. Addition of K+ formed sandwich type adducts with 15-crown-macrocycles diminishing aggregation of planar molecules by intramolecular rather
than intermolecular complexation.
Corresponding author. E-mail: ahmetg@itu.edu.tr
Received May 23, 2002; accepted (revised) May 31, 2002 相似文献
3.
Yu. B. Ivanova V. B. Sheinin N. V. Chizhova 《Russian Journal of Coordination Chemistry》2006,32(9):639-643
The acid dissociation of tetraphenylporphyrazine (H2PA(Ph)4) and octa(4-bromophenyl)porphyrazine (H2PA(4-BrPh)8) and their reactions with Cd2+ ions were studied in DMSO at 298 K. The equilibrium formation constants of the complexes and the acid dissociation constants of porphyrins were calculated; their relationship with the stability constants of the complexes was analyzed. The acidity sequence for porphyrazine derivatives was established. 相似文献
4.
Ergün Gonca 《高分子科学杂志,A辑:纯化学与应用化学》2017,54(9):589-597
The reaction of (5-hydroxypentylthio magnesium porphyrazine) with 2-methoxy-4,6-bis(trifluoromethyl)benzoic acid in DCCI and PTSA, esterified MgPz having [5-thiopentyl 2-methoxy-4,6-bis(trifluoromethyl)benzoate] substituent was obtained. Further reactions of the metal-free porphyrazine with M2+(Mg, Co, Cu, Zn, Fe) acetates have produced the metallo-porphyrazines. Finally, by the reaction of FePzCl with pyridine or pyrazine compounds, [FePz(py)2] and [FePz(pyz)]n complexes were prepared as the novel stable complexes, respectively. The target compounds have been characterized by using different spectroscopic methods such as FT-IR, UV-Vis, mass, 1H, 13C, and 19F NMR together with elemental analysis. The aggregation and the solubility features were indicated in various concentrations and solvents. 相似文献
5.
Density functional theory (DFT) calculations were carried out to investigate the organic field effect transistor (OFET) performance
of the symmetrical metal-free tetrakis (1,2,5-thiadiazole) porphyrazine (S4)PzH2 and tetrakis (1,4-diamyloxybenzene) (A4)PzH2 as well as the low-symmetry metal-free porphyrazine with annulated 1,2,5-thiadiazole and 1,4-diamyloxybenzene groups in the
ratio 2:2 (cis) and 1:3, that is, (cis-S2A2)PzH2 and (SA3)PzH2, (S = 1,2,5-thiadiazole ring, A = annulated 1,4-diamyloxy-benzene ring, Pz = porphyrazine) in terms of the highest occupied
molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy, ionization energy (IE), electron affinity
(EA), and their reorganization energy (λ) during the charge-transport process. On the basis of Marcus electron transfer theory, electronic couplings (V) and field effect transistor (FET) properties for the four compounds with known crystal structure have been calculated. The
electron transfer mobility (μ−) is revealed to be 0.056 cm2·V−1·s−1 for (S4)PzH2. The hole transfer mobility (μ+) is 0.075, 0.098, and 8.20 cm2·V−1·s−1 for (cis-S2A2)PzH2, (SA3)PzH2, and (A4)PzH2, respectively. The present work represents the theoretical effort towards understanding the OFET properties of symmetrical
and unsymmetrical porphyrazine derivatives with annulated 1,2,5-thiadiazole and 1,4-diamyloxybenzene.
Supported by the National Natural Science Foundation of China (Grant No. 50673051) and Beijing Municipal Commission of Edueation 相似文献
6.
《Journal of Coordination Chemistry》2012,65(1):162-175
Metal-free and metallo-porphyrazines (M?=?Mg, Co, Cu, Zn, and ClFe) carrying eight hydroxybutylthio groups at peripheral positions were prepared from 2,3-bis(4-hydroxybutylthio) maleonitrile. The hydroxybutyl groups were incorporated by esterification of porphyrazine derivatives with 4-biphenylcarboxylic acid in the presence of dicyclohexylcarbodiimide and p-toluenesulfonic acid. Unlike the parent porphyrazine, the symmetrically functionalized porphyrazines with eight ester units were soluble in common organic solvents such as chloroform, dichloromethane, tetrahydrofuran, acetone, and toluene and insoluble in water and n-hexane. Chloro-octakis(4-thiobutyl 4-biphenylcarboxylate) porphyrazinato iron(III) (FePzCl) was prepared by the reaction of metal-free porphyrazine with iron(II) acetate and further treatment with HCl solution. The monomeric bisaxial complex [FePz(py)2] and the bridged complex [FePz(pyz)]n were formed as stable complexes by reacting FePzCl with pyridine and pyrazine, respectively. The newly synthesized compounds were characterized by elemental analysis, FT-IR, UV?vis, mass, 1H and 13C NMR spectroscopy. 相似文献
7.
E. S. Taraimovich P. A. Stuzhin O. I. Koifman 《Russian Journal of General Chemistry》2013,83(2):392-397
Acid-base properties of Al(III), Ga(III), and In(III) complexes with tert-butyl-substituted thianaphthene-annulated porphyrazine and tetra(2,3-pyrazino)porphyrazine in proton-donor medium (CH2Cl2-CF3COOH) were studied by spectrophotometric titration. The concentration stability constants of the singly protonated complexes were determined. The effects of the metal nature and aromatic heterocyclic fragment on the basicity of meso-nitrogen atoms were analyzed. Negative inductive effect of the sulfur atom in the thianaphthene fragment reduces the basicity of the meso-nitrogen atoms as compared to analogous porphyrazine and phthalocyanine complexes. Acid-base transformations of the thianaphthene-annulated tetra(2,3-pyrazino)porphyrazine involve both meso-nitrogen atoms and those in the pyrazine rings. 相似文献
8.
《Monatshefte für Chemie / Chemical Monthly》2003,33(2):11-21
In this study, the electrochemical properties of novel porphyrazines with eight crown ether substituents appending on the
periphery through flexible chains were investigated by using cyclic voltammetry and controlled potential coulometry. Cyclic
voltammetry measurements showed that the metal free porphyrazine gave all of the six possible redox reactions of common porphyrazine
derivatives. Cobalt porphyrazine exhibited a metal-based reduction and a metal-based oxidation processes followed by two ligand-based
reduction and two oxidation processes. I
p vs. ν1/2 plots of redox processes of the two compounds indicated the diffusional mass transfer mechanism of the complexes. Copper
porphyrazine gave an oxidation process having adsorption properties and three reduction reactions. The variations of peak
current ratios of electrochemical reactions for all three complexes with scan rate showed that electron transfer processes
of complexes were followed by reversible or irreversible chemical reactions. Aggregation and sandwich adduct formation properties
of complexes were determined by CV measurements. Peak potentials of redox processes for all complexes were shifted towards
positive potentials by addition of alkali metal cations. Addition of K+ formed sandwich type adducts with 15-crown-macrocycles diminishing aggregation of planar molecules by intramolecular rather
than intermolecular complexation. 相似文献
9.
The photogeneration of the singlet molecular oxygen (1O2) by copper tetra(4-tert-butyl) phthalocyanine in organic solvents of different nature was substantiated. The apparent quantum yields of 1O2in benzene and pyridine were determined. The data obtained indicate an influence of the coordinating properties of the solvent
on the 1O2yield. However, this factor is not “critical” as in the case of photogeneration of 1O2by copper tetra(5-tert-butylpyrazino)porphyrazine. 相似文献
10.
The energy and nucleus‐independent chemical shift (NICS) of 95 isomers of N‐confused porphyrazine (NCPz), including normal porphyrazine (N0CPz), N‐confused porphyrazine (N1CPz), doubly N‐confused porphyrazine (N2CPz), triply N‐confused porphyrazine (N3CPz), and fully N‐confused porphyrazine (N4CPz), have been calculated by the density‐functional theory (DFT) method. The stability of NCPz decreased by increasing the number of confused pyrrole rings and the macrocycle tend to be destabilized stepwise by approximately +21 kcal/mol. The relative energies of the most stable isomers in confusion level are 0 kcal/mol (N0CPz‐1), +23.481 (N1CPz‐5), +41.849 (N2CPz‐a4), +61.738 (N3CPz‐b3), and +84.596 (N4CPz‐b13), respectively. The most stable isomers of N2CPz, N3CPz, and N4CPz are not necessarily the most aromatic but rather nonaromatic, especially in the case of N3CPz and N4CPz. On the other hand, the magnitude of the aromaticity estimated by NICS for these isomers does not differ largely. The NICS values of the most aromatic isomers are ?15.5411 (N0CPz‐1), ?14.0458 (N1CPz‐2), ?12.8171 (N2CPz‐d1), ?11.5961 (N3CPz‐b6), and ?12.8012 ppm (N4CPz‐a6), respectively. © 2009 Wiley Periodicals, Inc. Int J Quantum Chem, 2010 相似文献
11.
Shi-Zheng Zhu 《Heteroatom Chemistry》1994,5(1):9-18
Phenyliodonium bis(perfluoroalkanesulfonyl) methides PhI+ −C(SO2RF)2 ( 3 ) were prepared by the reaction of bis(perfluoroalkanesulfonyl)methanes with diacetoxyiodobenzene. The photochemical reactions of 3 with alkenes, methanol, bromine, and benzene gave the corresponding addition or insertion products. When 3 was irradiated in the presence of methyl sulfide, pyridine, and triphenylphosphine, it afforded the ylides containing the bis(perfluoroalkanesulfonyl)methylene functionality, Y+ −C(SO2RF)2. In these reactions the bis(perfluoroalkanesulfonyl)carbene intermediate (RFSO2)2C: may be involved. Irradiation or heating of 3 in DMSO gave a 1 : 1 complex, the structure of which was confirmed by X-ray diffraction analysis. Bis(perfluoroalkanesulfonyl)-methylene dimethyloxosulfonium ylides Me2(O)S+ −C(SO2RF)2 were obtained by air oxidation of bis(perfluoroalkanesulfonyl)methylene dimethylsulfonium ylides. 相似文献
12.
用DFT方法计算分析了1,2,5-噻重氮和1,4-二正戊氧基苯环化的自由四氮杂卟啉及其金属镁配合物的分子和电子结构,理论计算的键参数和单晶结构测定结果一致。进一步对1,2,5-噻重氮和1,4-二正戊氧基苯环化的自由四氮杂卟啉的红外光谱进行了正则坐标分析和光谱模拟,以及用TD-DFT方法对1,2,5-噻重氮和1,4-二正戊氧基苯环化的四氮杂卟啉金属镁配合物的电子吸收光谱进行了分析和谱峰归属,比较了四氮杂卟啉环上取代基的电子性质对四氮杂卟啉衍生物光谱性质的影响。 相似文献
13.
《Journal of Coordination Chemistry》2012,65(6):1093-1106
The syntheses of platinum(II) complexes of bis(dimethylphosphinylmethylene)amine and bis(aminomethyl)phosphinic acid were investigated. In the case of bis(dimethyl-phosphinylmethylene)amine the reaction with K2[PtCl4] yields the potassium amino-trichloroplatinate K[PtCl3L] (L?=?bis(dimethylphosphinylmethylene)amine), which was characterized by multinuclear (1H, 13C, 31P, and 195Pt) NMR spectroscopy in solution. Bis(aminomethyl)phosphinic acid reacts with K2[PtCl4] under strictly controlled pH conditions to give colorless crystals of the cisplatin analog K[PtCl2L′] (L′?=?bis(aminomethyl)phosphinate). This complex was characterized by multinuclear NMR spectroscopy in solution as well as by single-crystal X-ray diffraction in the solid state. The bis(aminomethyl)phosphinate coordinates to platinum via both amino functions, thus acting as a chelating ligand. 相似文献
14.
David H. Williamson Catherine Santini-Scampucci Geoffrey Wilkinson 《Journal of organometallic chemistry》1974,77(2):C25-C26
Interaction of trimethyldichlorotantalum with potassium bis(pyrazolyl)borate, K+[pz2BH2]—, gives the chloride-free complex Me3Ta(pz2BH2)2; other examples of similar reactions are reported. 相似文献
15.
A. A. Gaberkorn I. A. Popkova P. A. Stuzhin C. Ercolani 《Russian Journal of General Chemistry》2006,76(9):1494-1503
Basic properties of tri(4-tert-butylbenzo)[b,g,l](1,2,5-thiadiazolo)[3,4-q]porphyrazine and its Cu complex in the H2SO4-CH3COOH medium were studied by means of spectrophotometric titration. It was found that in going from an acetic acid solution 100% H2SO4 the complete acid-base interaction consecutively involves all the four meso-nitrogen atoms of the porphyrazine macroring, as well as one of the nitrogen atoms of the 1,2,5-thiadiazol fragment. The stability constants of the resulting acid forms were determined and compared with the gas-phase proton affinities calculated by the AM1 method. Annulation of a 1,2,5-thiadiazole fragment to the porphyrazine macroring increases the basicity of the 1,2,5-thiadiazole nitrogen atoms and decreases the basicity of macroring meso-nitrogen atoms. 相似文献
16.
《Acta Crystallographica. Section C, Structural Chemistry》2018,74(4):442-451
Metallocene dihalides and derivatives thereof are of great interest as precursors for catalysts in polymerization reactions, as antitumor agents and, due to their increased stability, as suitable starting materials in salt metathesis reactions and the generation of metallocene fragments. We report the synthesis and structural characterization of a series of eleven substituted bis(η5‐cyclopentadienyl)titanium dihalides, namely bis[η5‐1‐(diphenylmethyl)cyclopentadienyl]difluoridotitanium(IV), [Ti(C18H15)2F2], bis{η5‐1‐[bis(4‐methylphenyl)methyl]cyclopentadienyl}difluoridotitanium(IV), [Ti(C20H19)2F2], and bis{η5‐1‐[bis(adamantan‐2‐yl)methyl]cyclopentadienyl}difluoridotitanium(IV), [Ti(C15H19)2F2], together with the bromide and iodide analogues, and the chloride analogues of the diphenylmethyl and adamantyl complexes. These eleven complexes were prepared by the reaction of the corresponding bis(η5:η1‐pentafulvene)titanium complexes with different hydrogen halides (Cl, Br and I). The titanocene fluorides become available via chloride–fluoride exchange reactions. 相似文献
17.
Three bis‐acylamide compounds, N1,N4‐bis(pyridin‐4‐yl)‐cyclohexane‐1, 4‐dicarboxamide ( L1 ), 1, 1′‐(1, 3‐phenylenedicarbonyl‐)bis(1H‐1, 2, 3‐benzotriazole) ( L2 ), and N1,N4‐bis(1H‐1, 2, 4‐triazole) phthalamide ( L3 ) were synthesized. L1 , L2 , and a CuII complex based on L3 formulated as CuCl2( L3 )2(en)2 ( 1 ) (en = ethylenediamine) were structurally characterized by single‐crystal X‐ray diffraction for the first time. L1 , L2 , and L3 exhibit different photoluminescence properties. 相似文献
18.
James A.S. Howell Jack Lewis Trevor W. Matheson David R. Russell 《Journal of organometallic chemistry》1975,99(3):C55-C58
1,2-Cyclononadiene reacts with Fe2 (CO)9 with dimerization of the allene ligand to give the bis(π-allylene)Fe2 (CO)6 complex, which 13C and 1H NMR studies show to be fluxional. 相似文献
19.
Nasim Asghari Lalami Hassan Hosseini Monfared Hashem Noei Peter Mayer 《Transition Metal Chemistry》2011,36(6):669-677
Three new binuclear vanadium(V) complexes of bis(aryl)adipohydrazones (H4L1 = bis((2-hydroxynaphthalen-1-yl)methylene)adipohydrazide, H4L2 = bis(5-bromo-2-hydroxybenzylidene)adipohydrazide, and H4L3 = bis(2-hydroxy-3-methoxybenzylidene)adipohydrazide) were synthesized by direct reaction of [VO(acac)2] with the hydrazone ligands. The ligands and complexes were characterized by FT–IR, UV–Vis, and NMR spectroscopic methods.
The crystal structures of the complexes of L1 and L3 were determined by X-ray analyses. The solid-state structure of the complex of L1 features a 1D hydrogen-bonded chain from N⋯H–O hydrogen bonding. The catalytic activities of these complexes have been tested
in the oxidation of various hydrocarbons using H2O2 as the terminal oxidant. Generally, good to excellent conversions have been obtained. 相似文献
20.
Magnesium porphyrazine having eight 5-hydroxypentylthio groups at the peripheral positions, was synthesized from 2,3-bis(5-hydroxypentylthio) maleonitrile. By the esterification reaction of octakis(5-hydroxypentylthio) porphyrazinato] Mg(II) with 3,4,5-trimethoxybenzoic acid in dicyclohexylcarbodiimide and toluene-p-sulfonic acid, esterified MgPz appending [5-thiopentyl 2-methoxy-4,6-bis(trifluoromethyl) benzoate] substituent was obtained. Further reaction of the metal-free porphyrazine with Co(II), Cu(II), Zn(II), and Fe(II) acetates have produced the metallo-porphyrazines. By reacting FePzCl with pyridine or pyrazine, the monomeric bis-axial and the oligomeric complexes were synthesized as the novel stable complexes, respectively. Their characterizations were performed by using elemental analysis, FT-IR, 1H-NMR, 13C-NMR, mass and UV-Vis spectral data. The aggregation investigations carried out in different concentrations indicate that 3,4,5-trimethoxybenzyloxy-substituted porphyrazine compounds do not have any aggregation behavior in different concentrations. Quantum chemical computations were also done to the structural and electronic properties of target compounds. 相似文献