İsmail Gümrükçüoğlu

Experimental and quantum chemical computational study of (E)-1-[5-(3,4-dimethylphenyldiazenyl)-2-hydroxyphenyl]ethanone

In this work, the azo dye, (E)-1-[5-(3,4-dimethylphenyldiazenyl)-2-hydroxyphenyl]ethanone, has been synthesized and characterized by IR, and X-ray single-crystal determination. In the theoretical calculations, the stable structure geometry of the isolated molecule in gas phase was investigated under the framework of the density functional theory (B3LYP) with 6-31G (d, p). To designate lowest energy molecular conformation of the title molecule, the selected torsion angle was varied every 10° and the molecular energy profile was calculated from -180° to +180°. Besides, molecular electrostatic potential (MEP), frontier molecular orbitals (FMO) analysis, and thermodynamic properties were described from the computational process. In addition to these calculations, we were investigated solvent effects on the nonlinear optical properties (NLO) of the title compound.

An Investigation of 13C-NMR Spectra of Some Intramolecular Hydrogen Bonded and Non-Bonded Azo Dyes

Abstract The 13C-NMR spectra of the azo dyes which were synthesized by reacting substituted benzenediazonium chloride with derivatives of some phenol have been measured. The spectral data of these compounds were described considering intramolecular hydrogen bond and not. The chemical shift assignments were made regarding substituent effects.

(E)-2-Acetyl-4-[(3-methyl-phenyl-)diazen-yl]phenol: an X-ray and DFT study.

The title compound, C15H14N2O2, an azo dye, displays a trans configuration with respect to the N=N bridge. The dihedral angle between the aromatic rings is 0.18 (14)°. There is a strong intramolecular O—H⋯O hydrogen bond. Geometrical parameters, determined using X-ray diffraction techniques, are compared with those calculated by density functional theory (DFT), using hybrid exchange–correlation functional, B3LYP and semi-empirical (PM3) methods.

Synthesis and Characterization of Phthalocyanines Containing Eight Azamacrocycle Groups

Abstract Metal-free and metal phthalocyanines (H2, Cu, Ni, Co and Fe) with eight 12-membered tetraaza macrocycle complexes have been synthesized and characterized by elemental analyses, IR, 1H NMR and UV-VIS spectroscopy and thermogravimetric analysis.

ELECTRON SPIN RESONANCE STUDIES OF THE RADICALS OF (Ar′O)2P(S)Cl AND (Ar″O)3P=S INDUCED BY GAMMA IRRADIATION (Ar′=2,6-DIMETHYLPHENYL AND 2-TERT-BUTYLPHENYL Ar″=2-ISO-PROPYL-5-METHYLPHENYL)

Abstract A newly synthesized and dedected stable thiophosphorylradicals, bis(2,6-dimethylphenoxy)thiophosphoryl and bis(2-tert-butylphenoxy)thiophosphosphoryl and alkyl radical have been observed in gamma irradiated bis(2,6-dimethylphenyl)chlorothiophosphate and bis(2-tert- butylphenyl)chlorothiophosphate and tris(2-iso-propyl-5-ethylphenyl)thiophosphate single crystals respectively. The characteristic feature is that the phosphorus hyperfine splitting are 26.76 G and 26.65 G respectively for two compounds, but the g values are very unisotropic varying between 1.9996 and 2.054. Tris(2-iso-propyl-5-methylphenyl)thiophosphate does not give phosphoryl radical on gamma irradiation. The radical observed is carbon-centered (alkyl) and forms after 1,6-hydrogen shift on isopropyl group towards sulphur atom giving methyl proton splitting with 15.86 G and a proton siplitting in the neighborhood with 5.5 G. The g value is measured to be 2.0025 for this radical.

1-{5-[(E)-(4-Propyl­phen­yl)diazen­yl]-2-hy­droxy­phen­yl}ethanone

The molecular geometry of the title compound, C17H18N2O2, displays an E configuration with respect to the azo group. The dihedral angle between the aromatic rings is 10.39 (4)°. In the molecule, an intramolecular O—H⋯O hydrogen bond generates an S(6) ring motif.

(E)-2-Hydr-oxy-6-[(4-propyl-phenyl)-iminiometh-yl]phenolate.

The title compound, C16H17NO2, crystallizes with three crystallographically independent zwitterionic molecules in the asymmetric unit which differ significantly in the orientations of the propyl side chains. The dihedral angles between the two benzene rings in the three molecules are 6.17 (7), 6.75 (7) and 23.67 (7)°, respectively. In each independent molecule, an intramolecular N—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal, each independent molecule exists as part of an O—H⋯O hydrogen-bonded centrosymmetric R 2 2(10) dimer.

(E)-2-[(2-Ethyl-phen-yl)iminiometh-yl]-6-hydroxy-phenolate.

The molecule of the title compound, C15H15NO2, crystallizes in a zwitterionic form, and displays an E configuration about the C=N bond. The dihedral angle between the two aromatic rings is 5.59 (6)°. An intramolecular N—H⋯O hydrogen bond generates an S(6) ring motif. In the crystal structure, pairs of molecules are linked into centrosymmetric R 2 2(10) dimers by pairs of O—H⋯O hydrogen bonds. Aromatic π–π interactions are observed between the benzene rings of adjacent dimers [centroid–centroid distance = 3.4808 (7) Å].

Structure of 5-Allyl-2-hydroxy-3-methoxyazobenzene

Abstract 5-allyl-2-hydroxy-3-methoxyazobenzene was preperad by the reaction of 4-allyl-2-methoxyfenol and benzenediazoniumchloride and crystallized from dimethylsulphoxide to yield crystals suitable for analysis. The molecular structure was identified by UV-VIS, IR, 1H-NMR, 13C-NMR and elemental analysis. The crystal structure of the title compound was determined as monoclinic by by single crystal X-Ray diffraction technique. The crystal parameters of this compound are as follows: monoclinic P 2 1/n, a=5.559(2) A,b=14.900(2) A, c= 17.573(29 A, P = 98.58(1)†, V = 1439.3(2) A3, Z = 2, Dx = 0.610 g/cm3, F(OOO) = 284, λ (MoKα) = 0.71070 A, μ = 0.041 mm−1. The structure was solved by SHELXS-86 and refined by SHELXL-93. R = 0.09 for 1107 observed reflections with I > 2σ (I).

1-{5-[(E)-(2-Fluoro-phen-yl)diazen-yl]-2-hy-droxy-phen-yl}ethanone.

Theere are two independent molecules in the asymmetric unit of the title compound, C14H11FN2O2, each with a trans configuration with respect to the azo double bond. The dihedral angle between the aromatic rings is 17.21 (2)° in one molecule and 19.06 (2)° in the other. Each of the independent molecules has an intramolecular O—H⋯O hydrogen bond. In the crystal, molecules are stacked along [100].