Theoretical investigation of the interaction between the metal phthalocyanine [MPc]a(M = Sc,Ti, and V; a = –1, 0, and +1) complexes and formaldehyde

Formaldehyde (FA, CH₂O) is one of the toxic volatile organic compounds that cause harmful effects on the human body. In this work, the interaction of FA gas with metal phthalocyanine (MPc) molecules was studied by employing density functional theory calculations. A variety of [MPc]^a (M = Sc, Ti, and V; a = –1, 0, and +1) complexes were studied, and the electronic properties, interaction energies, and charge transfer properties of all of the studied molecules were systematically discussed. Among the studied complexes, the Sc and Ti phthalocyanines were more reactive toward the adsorption of FA gas. Moreover, it was revealed that the interaction of the [ScPc]⁺¹ and [TiPc]⁰ complexes with the CH₂O molecule was stronger, in which the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy gap of 46% and 36% decreased after FA adsorption. The results indicated that the MPc-based materials may be a promising candidate for the detection of FA gas.     

酞菁,酞菁铁及酞菁镍电子性质的理论研究

以双片层分子为晶体单胞模型，用量子化学具有晶体轨道的ＥＨＭＯ方法研究了酞菁、酞菁铁及酞菁镍的导电性能，讨论了碘掺杂对它的影响。计算结果表明：由于碘掺杂后，系体构型发生了较大的变化，层间作用加强，从而前述几种晶体的能隙均显著降低，电导率大幅度提高。     

Pd（OAc）2／FePc催化环己烯氧化合成环己酮的研究

考察了几种Ｆｅ－大环配合物与Ｐｄ（ＯＡｃ）２组成的双组分催化体系，在乙腈酸性水溶液中环己烯经合成环己酮的催化活性，实验结果表明，其中以酞菁失（ＦｅＰｃ）与Ｐｄ（ＯＡｃ）２组成的催化体系活性最高，而ＦｅＴＰＰＣｌ与Ｐｄ（ＯＡｃ）２催化体系，虽然催化活性较高，但催化剂的稳定性较低，各种因素对Ｐｄ（ＯＡｃ）２／ＦｅＰｃ催化活催化影响的研究结果指出，在无水和酸存在的非水溶液中，Ｐｄ（ＯＡｃ）２／ＦｅＰｃ对     

Synthesis and photoconductivity study of phthalocyanine polymers. V. 4,4′-diamino-diphenyl ether bridged polymeric SiPc

A novel polymer with quasi-one-dimensional structure of 4,4′-diamino-diphenyl ether bridged polymeric silicon phthalocyanine ( I ) is synthesized by the condensation polymerization of 4,4′-diamino-diphenyl ether (DDE) monomer and dichloride silicon phthalocyanine (Cl₂SiPc) monomer. The structure of the polymer ( I ) is identified by IR subtraction and UV/VIS spectroscopy and elemental analysis. The photoconductivity of the polymer I with quasi-one-dimensional structure is better than that of not only the parent Cl₂SiPc reactant, but also other polymeric phthalocyanines without one-dimensional structures, and showing one-dimensional effect of molecular structure. © 1997 John Wiley & Sons, Inc.     

Synthesis and photoconductivity study of phthalocyanine polymers. IV. [SiPcNHCH2CH2NH]n

The preparation of a novel polymer of ethylenediamine bridged polymeric silicon phthalocyanine ( I ) with quasi-one-dimensional structure is described. The product was obtained by the condensation polymerization of ethylenediamine and silicon dichloride phthalocyanine (Cl₂SiPc) monomers and was characterized by IR and UV/VIS spectroscopy and elemental analysis. The photoconductivity of the polymer I with the quasi-one-dimensional structure is much better than that of not only the corresponding Cl₂SiPc monomer, but also other phthalocyanine polymers whose molecules are not one-dimensional structures, and showing the one-dimensional effects of molecular structure of increasing photoconductivity. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35: 959–964, 1997     

四(α-高歧化度烷氧基)酞菁合成关键步骤的研究

烷氧基邻苯二腈是酞菁合成的重要中间体,但高歧化度烷氧基邻苯二腈的合成由于副产物多,产率低下而成为此类酞菁应用的"瓶颈".文中对反应副产物进行了分离纯化,并利用红外、气质联用、1HMR和元素分析等测试手段对其进行了表征.且根据测试数据推导出了副产物结构式为1,2,1'2' 四腈基 3,3' 二苯基醚.这一副反应机制的阐明,对于寻求对主反应有利的条件,具有重要的意义.     

Selective enrichment of glycopeptides based on copper tetra(N‐carbonylacrylic) aminephthalocyanine and iminodiacetic acid functionalized polymer monolith

Efficient separation and enrichment of low‐abundance glycopeptides from complex biological samples is the key to the discovery of disease biomarkers. In this work, a new material was prepared by coating copper tetra(N‐carbonylacrylic) aminephthalocyanine and iminodiacetic acid onto poly(glycidyl methacrylate‐pentaerythritol triacrylate) monolith. The monolith was applied to polymer monolithic microextraction for specific capture of glycopeptides coupled with matrix‐assisted laser desorption/ionization time‐of‐flight mass spectrometry. The developed monolith exhibited satisfactory efficiency for glycopeptide enrichment with high selectivity and detection sensitivity. When the tryptic digest of immunoglobulin G was used as the sample, total 24 glycopeptides were identified and the detection limit was determined as 5 fmol. When the approach was applied to the analysis of glycopeptides in the mixture of bovine serum albumin and immunoglobulin G (100:1, m/m) digests, 16 glycopeptides could still be observed. Moreover, the monolith was successfully applied to the selective enrichment of glycopeptides from human serum digests, exhibiting great practicability in identifying low‐abundance glycopeptides in complex biological samples.     

Tetra‐ammonium Zinc Phthalocyanine to Construct a Graded 2D–3D Perovskite Interface for Efficient and Stable Solar Cells

The crystallographic defects inevitably incur during the solution processed organic‐inorganic hybrid perovskite film, especially at surface and the grain boundaries (GBs) of perovskite film, which can further result in the reduced cell performance and stability of perovskite solar cells (PSCs). Here, a simple defect passivation method was employed by treating perovskite precursor film with a hydrophobic tetra‐ammonium zinc phthalocyanine (ZnPc). The results demonstrated that a 2D‐3D graded perovskite interface with a capping layer of 2D (ZnPc)_0.5MA_n ? 1Pb_nI_3n + 1 perovskite together with 3D MAPbI₃ perovskite was successfully constructed on the top of 3D perovskite layer. This situation realized the efficient GBs passivation, thus reducing the defects in GBs. As expected, the corresponding PSCs with modified perovskite revealed an improved cell performance. The best efficiency reached 19.6%. Especially, the significantly enhanced long‐term stability of the responding PSCs against humidity and heating was remarkably achieved. Such a strategy in this work affords an efficient method to improve the stability of PSCs and thus probably brings the PSCs closer to practical commercialization.     

Extremely Photostable Electron-Deficient Phthalocyanines that Generate High Levels of Singlet Oxygen

A robust lead-mediated synthetic procedure for the generation of phthalocyanines substituted with electron-withdrawing groups has been developed. The free-base phthalocyanine and various metal complexes were prepared without discernible degradation of the peripheral electron-withdrawing substituents. Upon irradiation with red light, some of the thus-obtained metal complexes generated high levels of singlet oxygen. In particular, a palladium complex exhibited attractive photostability upon exposure to singlet oxygen as a bleaching agent. The photostability of such complexes that may manifest concomitantly to the generation of high levels of singlet oxygen was attributed to the presence of the electron-withdrawing groups, which results in energetically low-lying highest occupied molecular orbitals.     

Studies on tetra-amine phthalocyanines

Metal(II) tetranitro phthalocyanines of cobalt, nickel and copper are synthesized in pure state by a novel modified method. The complexes are characterized using elemental, electronic and IR spectral studies. Pure metal(II) tetra-amino phthalocyanines of cobalt, nickel and copper are synthesized by reducing the nitro groups of the above complexes using sodium sulphide. These complexes are also characterized by elemental, electronic, IR spectral and magnetic susceptibility measurements. The nature of the electrical conductivities of the above three metal(II) tetra-amino phthalocyanine derivatives are studied in the temperature range 303-473 K and the data are presented. Among the effect of various substituent groups on the electrical conducting property of phthalocyanine, amine group substituent on the peripheral benzene ring of the phthalocyanine molecule has been found to increase electrical conductivity to a greatest extent. These complexes showed about 10⁵-10⁶ times higher electrical conductivities compared to their parent phthalocyanine compounds.