Beytullah Ertem

The synthesis and characterization of a new metal-free phthalocyanine substituted with four diloop macrocyclic moieties

Abstract Symmetrically tetrasubstituted metal-free phthalocyanine 6 with four 14-membered dioxadithia macrocycles each of which is attached to a 15-membered crown ether has been prepared in a multi-step reaction sequence. The new compounds were characterized by elemental analysis, IR, 1 H and 13 C NMR, UV–vis and MS spectral data.

Synthesis and Characterization of Novel Metal-free and Metallophthalocyanines Containing 12-Membered Diazadioxamacrocycles

New metal-free phthalocyanines fused in peripheral positions with eight N-monotosylated diaza-12-crown-4 macrocyclic moieties connected by diethylenethio groups have been synthesized by cyclotetramerization of a newly synthesized dicyano-substituted macrocycle. Metallophthalocyanines were also prepared by reaction of the dicyano-substituted macrocycle in the presence of corresponding metal salts and a strong organic base. The new compounds were characterized by a combination of elemental analysis, 1H and 13C NMR, IR, electronic and mass spectroscopies.

Synthesis and characterization of novel metal-free phthalocyanines containing four cylindrical or spherical macrotricyclic moieties

Abstract The novel metal-free phthalocyanines 8 and 9 bearing four peripheral tetraaza-dithiahexaoxa cylindrical or spherical macrotricycles have been synthesized by tricyclo-tetramerization of isoindolinediimine derivatives of supercryptands 6 and 7 and were characterized by elemental analysis, 1 H and 13 C NMR, IR, MS and UV–vis spectral data.

The Synthesis and Properties of New Metal-free and Metallophthalocyanines Containing Four Diloop Macrocyclic Moieties

The synthesis and characterization of new metal-free (9) and metal-containing (Zn, Ni or Cu 10, 11, 12) derivatives of a symmetrically octasubstituted phthalocyanine derived from 21,22-dicyano-2,3,5,6,8,9,11,12,15,17,18,25,26,28-tetradecahydro[1,4,7,12] benzodioxadithiacyclotetradeceno[6,7-b][1,4,7,10,13]benzopentaoxacyclopentadecene (7), which was synthesized in a multi-step reaction sequence, have been described. The novel compouds have been characterized by a combination of elemental analysis, 1H and 13C NMR, IR, UV–vis and MS spectral data.

SYNTHESIS AND CHARACTERIZATION OF A NEW (E,E)-DIOXIME AND ITS MONO AND POLYNUCLEAR COMPLEXES CONTAINING A 14-MEMBERED DITHIADIAZA MACROCYCLIC MOIETY

A novel (E,E)-dioxime,5,6:13,14-di(4′-t-butylbenzo)-2,3-bis(hydroxyimino)-8,11-dithia-1,4-diazacyclotetradecane (H2L), containing a 14-membered dithiadiaza macrocyclic unit has been synthesized by the reaction of 1,2-bis(4-t-butyl-2-aminobenzylthio)ethane (1) and cyanogendi-N-oxide (2). A mononuclear nickel(II) complex (3) with a metal : ligand ratio of 1 : 2 was also prepared. A heterotrinuclear complex [Cu2Ni(HL)2](PF6)2 (4) was synthesized by using the mononuclear complex 3 and [Cu(CH3CN)4]PF6. A heteropentanuclear complex [Cu2(UO2)2(phen)2Ni(HL)2](PF6)2(NO3)2 (5) containing the oximato tetraanion as a bridging ligand and 1,10-phenanthroline as an end-capping ligand was obtained by using the heterotrinuclear ligand for the Cu2 center. The ligand and its complexes have been characterized by 1H and 13C NMR, IR and mass spectroscopy, elemental analysis and semiempirical quantum chemical calculations.

New peripherally tetra-[trans-3,7-dimethyl-2,6-octadien-1-ol] substituted metallophthalocyanines: synthesis, characterization and catalytic activity studies on the oxidation of phenolic compounds

Abstract In this paper, we elucidated the synthesis, characterization, and investigation of catalytic activity studies of new metallophthalocyanines 4 and 5 as the catalyst for phenolic compounds oxidation by trying different types of oxygen sources. The structural characterization of the products was made by a combination of elemental analysis, FT-IR, LC-MS/MS (for phthalonitrile derivative 3), MALDI-TOF mass spectral data (for metallophthalocyanines 4–7), UV–vis spectroscopy (for metallophthalocyanines 4–7), 1H NMR and 13C NMR spectroscopies (for compounds 3 and 6). The synthetic routes for the (trans-3,7-dimethyl-2,6-octadien-1-ol) substituted phthalonitrile derivative 3 and corresponding metallophthalocyanines 4–7 are outlined in Scheme 1. The MPc complexes 4–7 were synthesized via cyclotetramerization of compound 3 in the presence of the corresponding anhydrous metal salts (CoCl2 for 4, CuCl2 for 5, Zn(CH3COO)2 for 6 and MnCl2 for 7) in dry n-pentanol as solvent and 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as strong base at reflux temperature under nitrogen gas. Phthalocyanines and their metal complexes, in general, display poor solubility in most of the organic solvents, however, the synthesized metallophthalocyanine complexes 4–7 were highly soluble in common organic solvents because of the introduction of the methyl groups on alkyl chains of peripheral arms. The catalytic activity of compounds 4 and 5 was evaluated for the oxidation of phenolic compounds such as 4-nitrophenol, o-chlorophenol, 2,3-dichlorophenol, and p-methoxyphenol. CoPc 4 displayed good catalytic performance with a full oxidation of 4-nitrophenol into the corresponding benzoquinone and hydroquinone with the highest TON and TOF values within 3 h.

Synthesis and characterization of novel vic -dioxime and its mononuclear complexes containing tetraazadioxamacrobicyclic moieties

A (E, E)-dioxime, N,N′-bis(7-aminobenzo-17,23-dimethyl-4,11-dioxa-1,14,17,23-tetraazapentacyclo[12.10.100.5,10]hexadiconta-1,5,7,12,14-pentane)diaminoglyoxime (H2L) has been synthesized from (E, E)-dichloroglyoxime and 7-aminobenzo-17,23-dimethyl-4,11-dioxa-1,14,17,23-tetraazapentacyclo[12.10.100.5,10]hexadiconta-1,5,7,12,14-pentane which has been prepared from 7-nitro-17,23-dimethyl-4,11-dioxa-1,14,17,23-tetraazapentacyclo[12.10.100.5,10]hexadiconta-1,5,7,12,14-pentane. A mononuclear Ni(II) complex with a metal : ligand ratio of 1 : 2 was prepared and then a Ni(II) complex bridged with was obtained by reaction with boron trifluoride etherate. The structure of the dioxime and its transition metal complexes are proposed according to elemental analysis, 1H NMR, IR and mass spectral data.