Synthesis and spectral properties of lutetium complexes with unsymmetrical phthalocyanines and sandwich complexes based thereon containing tetraanthraquinonoporphyrazine fragments

Joint condensation of 4,5-bis(4-hexadecyloxyphenoxy)phthalonitrile (A) and tetrachlorophthalonitrile (B) in boiling hexan-1-ol in the presence of lithium hexan-1-olate and subsequent reaction with LuCl₃ · 6 H₂O gave single-decker lutetium complexes with unsymmetrical phthalocyanines (AABB, ABAB). Reactions of the latter with 9,10-dioxo-9.10-dihydroanthraquinone-2,3-dicarbonitrile afforded mixed-ligand double-decker lutetium complexes containing tetraanthraquinonoporphyrazine as one of the ligands. Spectral properties of the synthesized complexes were studied, and all complexes were found to exhibit red fluorescence.     

Synthesis and spectral properties of lanthanide double-decker complexes with tetrabenzoporphyrin and phthalocyanine

Mixed-ligand double-decker complexes containing tetrabenzoporphyrin and phthalocyanine fragments were synthesized by reaction of phthalocyanine dilithium salt with tetrabenzoporphyrin complexes of lutetium, dysprosium, gadolinium, neodymium, and lanthanum. A relation was found between spectral parameters of the obtained sandwich complexes and radii of the central metal ions.     

Synthesis and spectral properties of unsymmetrical benzoporphyrins containing phenoxy groups or quinoxaline fragments

Condensation of phthalimide and 4-tert-butylphthalimide with zinc(II) acetate gave 3-(3-oxo-2,3-dihydro-1H-isoindol-1-ylidenemethyl)-1H-isoindol-1-one and 5-tert-butyl-3-(5-tert-butyl-3-oxo-2,3-dihydro-1H-isoindol-1-ylidenemethyl)-1H-isoindol-1-one, respectively. Their reactions with 4-phenoxyphthalimide and quinoxaline-2,3-dicarboximide in the presence of Zn(OAc)₂ led to the formation of zinc complexes of cis-4,4′-diphenoxytetrabenzoporphyrin and cis-di(4-tert-butylbenzo)diquinoxalinoporphyrin. The complexes were converted into the free bases by treatment with sulfuric acid. Spectral properties of the obtained porphyrin derivatives were studied.     

Synthesis of unsymmetrical hydroxybenzylphenols containing isobornyl fragments

4-(Bromomethyl)-2,6-diisobornylphenol was synthesized from 2,6-diisobornyl-4-methylphenol through intermediate 4-bromo-2,6-diisobornyl-4-methylcyclohexa-2,5-dien-1-one. Reactions of 4-(bromomethyl)-2,6-diisobornylphenol with 2,6- and 2,4-dialkylphenols gave new 4-(hydroxybenzyl)phenol derivatives containing bulky tert-butyl and isobornyl substituents.     

Synthesis and spectral properties of europium phthalocyanine complexes

Methods for the synthesis of europium complexes with phthalocyanine and thenoyltrifluoroacetonate (tta) or ferrocenoyltrifluoroacetonate (fta) ligands are discussed. The spectral characteristics of the complexes PcEu(tta)(ttaH) and PcEu(fta)(ftaH) (Pc is phthalocyanine) are studied.     

Synthesis and spectral characteristics of phthalocyanines of unsymmetrical structure containing fragments of 3,6-didecyloxyphthalonitrile and 2-methyl-5,6-dicyanobenzimidazole

By alkylation of 3,6-dihydrooxyphthalonitrile with 1-bromodecane and by reaction of 4,5-diaminophthalodinitrile with acetic acid were synthesized respectively 3,6-didecyloxyphthalonitrile (A) and 2-methyl-5,6-dicyanobenzimidazole (B). The random condensation of the dinitriles obtained provided unsymmetrical phthalocyanines of A ₃ B, AABB, and AB ₃ type. Their spectral characteristics were investigated.     

The development of highly selective approaches to sandwich-type heteroleptic double- and triple-decker lutetium(III) and europium(III) phthalocyanine complexes

The selective synthesis of heteroleptic (heteronuclear) sandwich-type lanthanide phthalocyanines has been accomplished. Double-decker complexes ^BuPcLnPc, and ^BuPcLnPc^Cl (Ln = Lu, Eu; ^BuPc = 2,3,9,10,16,17,23,24-octabutylphthalocyaninate; Pc = phthalocyaninate, ^ClPc = 2,3,9,10,16,17,23,24-octachlorophthalocyaninate) were obtained in good yields by a direct interaction of metal-free ligand ^BuPcH₂ with the monophthalocyanines PcLnOAc or ^ClPcLnOAc. Heteronuclear triple-decker phthalocyanines PcEu^RPcLu^RPc, ^ClPcEu^RPcLu^RPc and ^BuPcEu^RPcLu^RPc (^RPc = ^BuPc, ^tBuPc; ^tBuPc = 2(3),9(10),16(17),23(24)-tetra-tert-butylphthalocyaninate) were obtained from the corresponding mono-(PcEuOAc, ^ClPcEuOAc, ^BuPcEuOAc) and bisphthalocyanines (^RPc₂Lu) under similar conditions.     

Synthesis and characterization of a new unsymmetrical porphyrin liquid crystal and its lanthanide complexes

A meso-substituted unsymmetrical porphyrin liquid crystal, 5-(4-myristyloxy)phenyl-10,15,20-triphenyl porphyrin, and a series of its lanthanide complexes, (lanthanide ions: Gd, Tb, Dy, Ho and Er) with acetylacetone were synthesized and characterized by elemental analyses, molar conductances, UV-Vis, IR and ¹H?NMR spectra. A structure is proposed in which the porphyrin is as a tetradentate ligand and acetylacetonate is bidentate to the lanthanide. Luminescence spectra show that quantum yields of the Q band fluorescence are in the region 0.027–0.191. DSC data and an optical textural photo using a polarizing microscope indicates that the compounds have liquid crystalline character.     

异双Schiff碱及其稀土配合物的合成、机理与波谱

利用2,6-二氨基己酸(赖氨酸)具有两端不对称结构的－NH~2基,合成了一端与水杨醛,另一端与2,4-二羟基苯甲醛缩合形成空间结构不对称的异双Schiff碱及其与稀土元素配合物。以元素分析、热分析、摩尔电导、红外光谱、EPR以及^1HNMR,^1^3C-^1HCOSY谱、固体高分辨^1^3C谱等表征,研究了这类不对称Schiff碱的形成机理和配位方式。     

New phosphorus-containing metal phthalocyanine complexes. Synthesis and spectral and electrochemical studies

Hitherto unknown phosphorus-containing 4,5-bis(diethoxyphosphorylmethyl)- and 4-methyl-5-diethoxyphosphorylmethylphthalonitriles were synthesized starting from o-xylene. Their tetramerization afforded free phthalocyanine ligands and their complexes with Zn, Ni, Co, and a number of rare-earth metals. The spectral and electrochemical properties of the phthalocyanines synthesized were studied. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1634–1638, August, 2008.     

Synthesis, mechanism and NMR spectra of lanthanide complexes with a novel unsymmetrical Schiff base

Owing to its two unsymmetrical-NH_2 groups sited on different terminals, 2, 6-diaminocaproic acid (lysine) was used as a reactant for synthesizing a novel unsymmetrical Schiff base with salicylaldehyde on one side and ovanillin on the other for the first time. It is a new way to synthesize such a special unsymmetrical Schiff base. It is named "hetero bis-Schiff base" for distinguishing it from others. The synthesis method, formation mechanism as well as twelve new lanthanide complexes with the above ligand are reported and discussed herein. They were characterized by elementary analysis, molar conductivity, IR-spectra and especially by ~1H and ~(13)C NMR spectra. The results obtained may provide a new promising method for synthesizing similar unsymmetrical Schiff bases and their complexes.     

Porphyrazines of symmetric and unsymmetrical structure with fused fragments of 1,4-bis(2-phenoxyethoxy)benzene and 5,6-diphenylpyrazine. Synthesis and spectral characteristics

By alkylation of 3,6-dihydroxyphthalonitrile with 1-bromo-2-phenoxyethane 3,6-bis(2-phenoxyethoxy) phthalonitrile was obtained. A random condensation of the nitrile with 2,3-dicyano-5,6-diphenylpyrazine in 1-butanol in the presence of lithium 1-butanolate porphyrazines were synthesized of symmetric and unsymmetrical structure, and their spectral characteristics were investigated.     

Synthesis and spectral characterization of lanthanide complexes with sulfamethoxazole and their antibacterial activity

A series of nonelectrolytic lanthanide(III) complexes, [ML₂Cl₃]·2H₂O, where M is lanthanum(III), praseodymium(III), neodymium(III), samarium(III), gadolinium(III), terbium(III), dysprosium(III), and yttrium(III), containing sulfamethoxazole ligand (L) are prepared. The structure and bonding of the ligand are studied by elemental analysis, magnetic susceptibility measurements, IR, ¹HNMR, TG/DTA, X-ray diffraction studies, and electronic spectra of the complexes. The stereochemistry around the metal ions is a monocapped trigonal prism in which four of the coordination sites are occupied by two each from two chelating ligands, sulfonyl oxygen, and nitrogen of the amide group and the remaining three positions are occupied by three chlorines. The ligand and the new complexes were tested in vitro to evaluate their activity against the bacteria Escherichia coli and Staphylococcus aureus. The text was submitted by the authors in English.     

Synthesis,spectral, and catalytic studies of ruthenium(II) unsymmetrical Schiff-base complexes

Unsymmetrically-substituted ruthenium(II) Schiff-base complexes, [Ru(CO)(B)(L ^x )] [B = PPh₃, AsPh₃ or Py; L ^x = dianion of tetradentate unsymmetrical Schiff-base ligand; x = 4–7, L⁴ = salen-o-hyac, L⁵ = valen-o-hyac, L⁶ = salphen-o-hyac, L⁷ = valen-2-hacn], were prepared and characterized by analytical, IR, electronic, and ¹H NMR spectral studies. The new complexes were tested for their catalytic activity towards the oxidation of benzylalcohol to benzaldehyde.     

Synthesis and spectral studies of platinum complexes with amide-group containing ligands

Summary Complexes of platinum(II) with 2-(acetylamino)benzoic acid, 2-(benzoylamino)benzoic acid, maleanilic acid, malea-1-naphthanilic acid, 2-(phenylamino)benzoic acid, 2-[(2-aminophenylamino)carbonyl]benzoic acid, 2-(aminobenzoyl)benzoic acid, 2-[1-naphthalenylamino)-carbonyl]benzoic acid, 2-(2-aminobenzoylamino)-benzoic acid have been prepared and characterized by elemental analysis, molar conductivity measurements, thermal data and i.r., electronic and n.m.r. spectra.     

Sandwich complexes of yttrium, neodymium, gadolinium, and dysprosium with meso-trans-di(hexadecyl)-tetrabenzoporphyrin and phthalocyanine fragments. Synthesis and spectral properties

Sandwich-type asymmetric complexes of yttrium, neodymium, gadolinium, and dysprosium were synthesized by the reaction of the corresponding meso-trans-bis(hexadecyl)tetrabenzoporphyrinates with dilithium phthalocyianine. Spectral properties of these compounds were investigated.     

不对称希夫碱卟啉及其稀土配合物的合成与表征

以二甲基甲酰胺为溶剂,5-对氨基苯基-10,15,20-三苯基卟啉与苯甲醛直接反应得到一种不对称希夫碱卟啉化合物,并合成了它的稀土配合物.用元素分析、紫外-可见光谱、红外光谱1、H核磁共振以及X射线光电子能谱对这些化合物进行了表征,推测了稀土乙酰丙酮卟啉配合物的结构,稀土离子与乙酰丙酮的两个O原子和卟啉的4个吡咯N原子配位,配位数为6,稀土离子位于卟啉平面的上方.