Synthesis, photophysical and thermal studies of symmetrical and unsymmetrical zinc phthalocyanines

The novel zinc phthalocyanine (3) with malonylester and chloro groups on each benzo unit was synthesized from 4-diethoxymalonyl-5-chloro-phthalonitrile (1). The unsymmetrically substituted zinc phthalocyanine (5), carrying hexylthio, malonylester and chloro groups at the periphery, was obtained from 4-diethoxymalonyl-5-chloro-phthalonitrile (1) and 4,5-bis-hexylsulfanyl-phthalonitrile (2) by a statistical condensation method as an A₃B type unsymmetrical phthalocyanine compound. Transesterification of the malonyl esters of the new symmetrical and unsymmetrical phthalocyanines occurred during the cyclotetramerization of dinitriles with Zn(CH₃COO)₂ in 1-pentanol in the presence of DBU. Octa-hexylthio-substituted zinc phthalocyanine (4) was prepared according to the literature. The photophysical and thermal properties of all the phthalocyanine complexes are described for the first time. These novel symmetrical and unsymmetrical phthalocyanine macrocycles have been characterized by a series of spectroscopic methods including ¹H NMR, electronic absorption, IR and mass spectroscopy, in addition to elemental analysis. Their narrow long wavelength absorption band shows that the bulky substituents on the periphery prevent aggregation. The unsymmetrically substituted phthalocyanine (5) gave a greater fluorescence quantum yield in chloroform than the symmetrical analogues (3 and 4).     

4-{[Mono/dimethyl(1,1'-biphenyl)-4-yl]oxy}phthalonitriles and Phthalocyanines Based on Them

4-{[Mono/dimethyl(1,1'-biphenyl)-4-yl]oxy}phthalonitriles have been obtained by nucleophilic substitution of nitro group in 4-nitrophthalonitrile. The prepared phthalonitriles have been used for the synthesis of tetra-4-{[mono/dimethyl(1,1'-biphenyl)-4-yl]oxy}phthalocyanines and their complexes with copper, cobalt, and zinc. Spectral characteristics and thermal stability of the prepared compounds have been investigated.     

Synthesis,photophysical and nonlinear optical properties of microwave synthesized 4-tetra and octa-substituted lead phthalocyanines

This work presents the photophysical and nonlinear optical behaviour of newly synthesized complexes: 2,(3)-tetrakis(4-benzyloxyphenoxyphthalocyaninato) lead (5a) and 2,3-octakis(4-benzyloxyphenoxyphthalocyaninato) lead (6a). The nonlinear optical behaviour of complexes 5a and 6a are compared with those of 2,(3)-tetraphenoxyphthalocyaninato lead (5b), 2,(3)-tetrakis(4-t-butylphenoxyphthalocyaninato) lead (5c), 2,3-octaphenoxyphthalocyaninato lead (6b) and 2,3-octakis(4-t-butylphenoxyphthalocyaninato) lead (6c). The synthesis of 5a and 6a was performed using microwave irradiation. Photophysical properties were studied for these complexes in dimethylsulfoxide, dimethylformamide, toluene, tetrahydrofuran and chloroform. The fluorescence spectra were different from excitation spectra due to demetallation upon excitation. High triplet quantum yields ranging from 0.80 to 0.86 (in DMSO, DMF and toluene) and low triplet lifetimes (20–50 μs in DMSO, and <10 μs in the rest of the solvents) were observed due to the presence of heavy atom. Nonlinear optical properties were studied in dimethylsulfoxide. The optical limiting threshold intensity (I_lim) for the PbPc derivatives were calculated and ranged from 2.1 to 6.6 W/cm².     

Phthalocyanines and related compounds: XLIII. Synthesis of poly[phenyl(alkyl)sulfanyl]-substituted phthalonitriles and some phthalocyanines based thereon

Nucleophilic substitution of chlorine atoms in tetrachlorophthalonitrile by benzene- and alkanethiols in the presence of a base was studied at different reactant ratios. The substitution is characterized by complete regioselectivity: the chlorine atom in position 4 of tetrachlorophthalonitrile is replaced first; next follows replacement of the 5-chlorine atom. The reactions of tetrachlorophthalonitrile with nucleophiles at ratios of 1:2 and 1:4 lead to the formation of the corresponding 3,6-dichloro-4,5-bis[phenyl(alkyl)sulfanyl]- and tetrakis[phenyl(alkyl)sulfanyl]phthalonitriles. The latter were converted into metal complexes of [phenyl-(alkyl)sulfanyl]-substituted phthalocyanines which absorb in the red and near-IR regions of the electronic spectra.     

Synthesis and liquic crystalline properties of copper tetra-4-(n-alkoxycarbonyl)phthalocyanines

Copper tetra-4-(n-alkoxycarbonyl)phthalocyanines were synthesized, and their thermotropic and lyotropic mesomorphism at different lengths of lateral substituents was studied. Their possibility of forming both thermotropic and lyophilic mesophases (amphotropy) was found. The length of lateral substituents affects the type of supramolecular packing in the mesophase rather than the temperature of the crystal→mesophase phase transition. A rarecase of the mesogeneity of disk-like compounds of the same chemical nature possessing only four substituents is discussed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 129–136, January, 2000.     

Phthalocyanines and related compounds: XLV. Nucleophilic substitution of chlorine in tetrachlorophthalonitrile: Synthesis of aryloxy-aubstituted phthalonitriles and phthalocyanines derived from them

Nucleophilic substitution of chlorine in tetrachlorophthalonitrile by the reaction with aryloxy anions is studied. Depending on the reactant ratio, the products of substitution of one, two, and/or three chlorine atoms are formed. Their tetramerization gives aryloxychloro-substituted phthalocyanines having the absorption band in the near-IR range.     

Synthesis and liquic crystalline properties of copper tetra-4-(n-alkoxycarbonyl)phthalocyanines

Copper tetra-4-(n-alkoxycarbonyl)phthalocyanines were synthesized, and their thermotropic and lyotropic mesomorphism at different lengths of lateral substituents was studied. Their possibility of forming both thermotropic and lyophilic mesophases (amphotropy) was found. The length of lateral substituents affects the type of supramolecular packing in the mesophase rather than the temperature of the crystal→mesophase phase transition. A rarecase of the mesogeneity of disk-like compounds of the same chemical nature possessing only four substituents is discussed. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 129–136, January, 2000.     

Synthesis and characterization of novel α- or β-tetra[6,7-dihexyloxy-3-(4-oxyphenyl)coumarin]-substituted metal-free and metallo phthalocyanines

The synthesis of novel phthalonitriles substituted at 3- or 4-position with 6,7-dihexyloxy-3-(4-oxyphenyl)coumarin were performed. The metal-free and metallo phthalocyanines (MPcs) (M = Zn, Co, Cu) were prepared by cyclotetramerization of 6,7-dihexyloxy-3-[p-(2′,3′-dicyanophenoxy)phenyl]coumarin or 6,7-dihexyloxy-3-[p-(3′,4′-dicyanophenoxy)phenyl]coumarin. The newly prepared compounds, phthalonitriles and Pcs, have been characterized by elemental analysis, ¹H NMR, ¹³C NMR, MALDI-TOF, IR, UV–Vis and fluorescence spectral data. The electronic spectra exhibit bands of coumarin identity along with characteristic Q and B bands of the Pc core. The IR-spectra of all Pcs showed three characteristic intense bands at 1709–1700 cm⁻¹ for lactone carbonyl, two bands at 1489–1604 cm⁻¹ for conjugated olefinic system.     

Phthalocyanines and related compounds: XLVII. Nucleophilic replacement of chlorine atoms in tetrachlorophthalonitrile. Synthesis of phenyl(alkyl)amino-substituted phthalonitriles and some phthalocyanines based thereon

Nucleophilic replacement of chlorine atoms in tetrachlorophthalonitrile by the action of primary and secondary amines was studied. The reactions of tetrachlorophthalonitrile with amines at a ratio of 1: 10 gave with high yields and regioselectivity the corresponding 4,5-diamino-3,6-dichlorophthalonitriles from cyclic secondary amines and 4-amino-3,5,6-trichlorophthalonitriles from primary amines and acyclic secondary amines. 4-Amino-3,5,6-trichlorophthalonitriles were used to synthesize cobalt and zinc phthalocyanine complexes. It was shown that replacement of chlorine atoms in the pyrrolic β-positions of hexadecachlorophthalocyanines by amino groups is not accompanied by red shift of the long-wave absorption band in the electronic spectra.     

Photophysical behaviour of asymmetrically substituted metal free, Mg and Zn phthalocyanines in the presence of folic acid

This work reports on the synthesis, characterisation and photophysical properties of new asymmetric metal free, magnesium and zinc phthalocyanines containing a mono carboxylic acid group for possible linking to biological molecules via an amide bond. Successful synthesis of the phthalocyanines was achieved through the statistical condensation method. The phthalocyanines were mixed with folic acid and their photophysical properties were examined. The triplet quantum yield values for all the complexes in DMSO were between 0.49 and 0.74 and in the presence of folic acid they were between 0.37 and 0.63. The lifetimes were generally good ranging from 70 to 290 μs in the absence or presence of folic acid.     

Nucleophilic substitution in 4-bromo-5-nitrophthalodinitrile: X. Synthesis of 4-(1-benzotriazolyl)-5-(1(2)-naphthyloxy)-phthalodinitriles and related phthalocyanines

4-(1-Benzotriazolyl)-5-[1(2)-naphthyloxy]phthalodinitriles were obtained by nucleophilic substitution of bromine and nitro group in 4-bromo-5-nitrophthalodinitrile. These compounds were used for the synthesis of the corresponding octa-substituted phthalocyanines. Spectral data of the compounds obtained were examined.     

Synthesis of n-(2-chloro-5-bromo-4-pyrimidyl)- and N-(2-chloro-5-iodo-4-pyrimidyl)amino acids

The previously unreported N-(2-chloro-5-bromo-4-pyrimidyl)- and N-(2-chloro-5-iodo-4-pyrimidyl) amino acids were synthesized.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 527–529, April, 1971.     

Synthesis and properties of tetra-4-morpholinyl(piperidinyl)-5-R-substituted phthalocyanines

Demetallation of magnesium tetra-4-morpholinyl(piperidinyl)-5-R-substituted phthalocyanines was performed to obtain the corresponding metal-free phthalocyanines. Their electronic absorption spectra were shown to depend on the nature of the solvent. It was found that both the saturated heterocycle and the oxyaryl substituent have almost no effect on the position of the absorption maximum.     

Synthesis and solvent effects on the electronic absorption and fluorescence spectral properties of substituted zinc phthalocyanines

The synthesis and spectroscopic properties of the following tetra- and octa-substituted aryloxy zinc(II) phthalocyanines are reported for the first time: 1,(4)-(tetrabenzyloxyphenoxyphthalocyaninato) zinc(II) (7); 2,(3)-(tetrabenzyloxyphenoxyphthalocyaninato) zinc(II) (8); 2,3-(octabenzyloxyphenoxyphthalocyaninato) zinc(II) (9). The new compounds have been characterized by elemental analysis, IR, ¹H NMR spectroscopy and electronic spectroscopy. Spectroscopic properties of these compounds were investigated in different solvents. Protonation of non-peripherally substituted complex 7 resulted in the splitting and red-shifting of the Q-band. The peripherally substituted derivatives 8 and 9, did not show the split in the Q-band. Fluorescence spectra of the derivatives show Stokes shifts typical of MPc complexes.     

The syntheses and photophysical properties of 4,4′-isopropylidendioxydiphenyl substituted ball-type dinuclear Mg(II) and Zn(II) phthalocyanines

The syntheses of ball-type dinuclear Zn(II) and Mg(II) phthalocyanines containing four 4,4′-isopropylidendioxydiphenyl substituents at the peripheral and non-peripheral positions are presented. The structures of the synthesized compounds were characterized using elemental analyses, and UV-Vis, FT-IR, ¹H NMR and mass spectroscopies. The Φ_F values were 0.14, 0.11, 0.22, 0.15 and Φ_T values were 0.84, 0.88, 0.62, 0.74, for 6-9, respectively. The largest triplet yields were observed for the non-peripherally substituted complexes 6 and 7, showing that non-peripheral substitution favors increased population of the triplet state. All complexes showed reasonably long triplet lifetimes with τ_T 510, 310, 910 and 350 μs in DMSO, respectively.     

Nucleophilic Substitution in 4-Bromo-5-nitrophthalodinitrile: V. Synthesis of 5-Nitro-4-(4-R-phenoxy)phthalodinitriles and Phthalocyanines Derived from Them

A series of aryloxy-substituted phthalodinitriles were prepared by nucleophilic aromatic substitution of bromine in 4-bromo-5-nitrophthalodinitrile, and the corresponding phthalocyanines were synthesized. The physicochemical properties of phthalocyanines depend on the substituent in the aryl moiety.     

Synthesis and Crystal Structure of 2-Amino-4- chloro-5-（4-methylbenzyl）-6-methylpyrimidine

The title compound 2-amino-4-chloro-5-(4-methylbenzyl)-6-methylpyrimidine (C26H28Cl2N6, Mr = 495.44) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. The crystal belongs to monoclinic, space group P21/c with a = 14.892(7), b = 6.129(3), c = 14.889(7) , β = 109.795(8)°, V = 1278.7(10) 3, Z = 2, F(000) = 520, Dc = 1.287 g/cm3, μ = 0.280 mm-1, the final R = 0.0577 and wR = 0.1589 for 1357 observed reflections with I > 2σ(I). A total of 6091 reflections were collected, of which 2257 were independent (Rint = 0.033). The X-ray analysis reveals that the chlorine atom and methyl of the title compound are disordered.     

1-(4-硝基苯基)-3-(5-氯吡啶)三氮烯的合成及其与锌的显色反应

报道了 1 ( 4 硝基苯基 ) 3 ( 5 氯吡啶 )三氮烯 (NPCPDT)的合成及其与锌的显色反应研究。在TX 1 0 0的存在下 ,pH 1 1 0的Na2 B4 O7 NaOH缓冲溶液中 ,该试剂能与锌发生显色反应 ,锌与NPCPDT形成摩尔比为 1∶2型的黄色配合物 ,在 440nm处有一最大正吸收 ,在 5 3 5nm处有一最大负吸收。以 440nm为参比波长 ,5 3 5nm为测量波长进行双波长测定 ,表观摩尔吸光系数为2 42× 1 0 5L·mol- 1·cm- 1,锌的质量浓度在 0～ 0 48μg/mL范围内符合比尔定律。用拟定方法测定人发中的微量锌 ,结果满意     

Synthesis and characterization of novel flavonoid-substituted phthalocyanines using (±)naringenin

In this study, novel unsymmetrical mono- and di-substituted metal free and metallo phthalocyanines containing peripheral naringeninoxy moieties have been prepared. The naringenin-substituted phthalonitrile was synthesized from 4-nitrophthalonitrile and (±)naringenin in dimethylsulfoxide. Preparation of unsymmetrical mono- and di-substituted phthalocyanines, 2-naringenin-7-O-phthalocyaninatozinc, 2,9-bis-naringenin-7-O-phthalocyaninatozinc, 2,9-bis-naringenin-7-O-phthalocyaninatocobalt and 2,9-bis-naringenin-7-O-phthalocyanine was performed at 120-140 °C using the corresponding phthalonitrile in the presence of N,N-dimethylethanolamine (DMAE), ZnCl₂, CoCl₂ and LiCl, respectively. Synthesized new phthalocyanine compounds have been characterized by elemental analysis and ¹H NMR, ¹³C NMR, FT-IR, MS and UV-vis spectroscopy. These are the first known examples of flavonoid-substituted phthalocyanines.     

The structure of the agrochemical fungicidal 4-chloro-3-(3,5-dichlorophenyl)-1H-pyrazole (RPA 406194) and related compounds

The difficulties to obtain convenient monocrystals of the important fungicide RPA 406194 have been overcome by a combination of solid state ¹³C NMR, X-ray powder diffraction and molecular modeling. The compound, a 3-aryl tautomer, crystallizes forming infinite chains of molecules bonded by N-H?N hydrogen bonds, leading to needle-shaped crystals. The tautomerism (equilibrium constant and energy barrier) of this compound in solution has been studied.