scholarly journals Alkyl 2-Benzothiazolyl Sulfide Ligated Dirhenium Complexes: Syntheses, Structure and Computational Study of [Re2(CO)8{μ,η1,η1-(R)SCNSC6H4}] (R = CH3 and C2H5)

2021 ◽  
Author(s):  
Md. Wahidul Islam ◽  
Joyanta K. Saha ◽  
Nikhil C. Bhoumik ◽  
Shafikul Islam ◽  
Md. Manzurul Karim
Keyword(s):  
Crystal Packing ◽  
Computational Study ◽  
Energy Levels ◽  
Spectroscopic Method ◽  
Diffraction Method ◽  
Dft Method ◽  
X Ray ◽  
Dirhenium Complexes ◽  
Elemental Analyses ◽  
Homo And Lumo

Abstract The synthesis of dirhenium complexes of 2-(methylthio)benzothiazole and 2-(ethylthio)benzothiazole and their X-ray crystal structures are reported. The complexes, [Re2(CO)8{μ,η1,η1-(CH3)SCNSC6H4}] (1) and [Re2(CO)8{μ,η1,η1-(C2H5)SCNSC6H4}] (2) are isolated as orange crystals from the easy displacement of acetonitrile from the labile complex, [Re2(CO)8(MeCN)2] in moderate yields. The complexes were characterized by elemental analyses and spectroscopic method, and their structures were determined by single crystal X-ray diffraction method. The optimized bond lengths and bond angles of the complexes using DFT method are in good agreement with experimental X-ray crystallographic data. The HOMO and LUMO energy levels of complexes 1 and 2 were studied with the help of DFT method, and their energy gaps were found 3.08 and 3.13 eV, respectively. The Hirshfeld surface analysis was performed to study the intermolecular interaction, crystal packing, and identification of close contacts in both complexes.

Preparation, structure, and electrochemistry of porphyrinato titanium (IV) benzenedithiolates with a trithiole ring, a dithiin ring, and two 2-cyanoethylthio groups

2018 ◽  
Vol 22 (01n03) ◽  
pp. 157-164
Author(s):  
Takeshi Kimura ◽  
Yusuke Muraoka ◽  
Kaori Amano ◽  
Toshiyuki Fujio ◽  
Takao Nishikawa ◽  
...  
Keyword(s):  
Gold Electrode ◽  
Chemical Shifts ◽  
Energy Levels ◽  
Dft Method ◽  
Similar Reaction ◽  
X Ray Crystallography ◽  
Cesium Hydroxide ◽  
Homo And Lumo ◽  
Related Compounds ◽  
Homo And Lumo Energy

The reaction of tetra([Formula: see text]-tolyl)porphyrinato titanium (IV) oxide (2) with 4,7-diethyl-5,6-dimercaptobenzo[1,2,3] trithiole (3a) produced the corresponding titanium (IV) complex, tetra([Formula: see text]-tolyl)porphyrinato titanium (IV) trithiolobenzenedithiolate (4a), fused with a trithiole ring. Related compounds 4b and 4c were prepared by a similar reaction of 2 with 5,8-diethyl-6,7-dimercaptobenzo[1,4]dithiin (3b) and 3,6-diethyl-4,5-dimercapto-1,2-bis(2-cyanoethylthio)benzene (3c). The structure of 4b was determined by X-ray crystallography. Compound 4c was further treated with cesium hydroxide to produce the corresponding dithiolate anion 4c2S, which was deposited on the gold electrode. The electrochemical property of the gold electrode was determined by cyclic voltammetry. The structure of simplified model compound 4b[Formula: see text] was optimized using the DFT method with the Gaussian 09 program. The optimized structure was utilized to calculate the NMR chemical shifts, the HOMO and LUMO energy levels, and the electronic transition in the absorption spectrum.

A complementary experimental and computational study of loxapine succinate and its monohydrate

2013 ◽  
Vol 69 (11) ◽  
pp. 1273-1278 ◽  
Author(s):  
Rajni M. Bhardwaj ◽  
Blair F. Johnston ◽  
Iain D. H. Oswald ◽  
Alastair J. Florence
Keyword(s):  
Succinic Acid ◽  
Powder Diffraction ◽  
Density Functional ◽  
Crystal Packing ◽  
Computational Study ◽  
Geometry Optimization ◽  
Global Optimum ◽  
X Ray Diffraction ◽  
X Ray ◽  
Fixed Cell

The crystal structures of loxapine succinate [systematic name: 4-(2-chlorodibenzo[b,f][1,4]oxazepin-11-yl)-1-methylpiperazin-1-ium 3-carboxypropanoate], C18H19ClN3O+·C4H5O4−, and loxapine succinate monohydrate {systematic name: bis[4-(2-chlorodibenzo[b,f][1,4]oxazepin-11-yl)-1-methylpiperazin-1-ium] succinate succinic acid dihydrate}, 2C18H19ClN3O+·C4H4O42−·C4H6O4·2H2O, have been determined using X-ray powder diffraction and single-crystal X-ray diffraction, respectively. Fixed cell geometry optimization calculations using density functional theory confirmed that the global optimum powder diffraction derived structure also matches an energy minimum structure. The energy calculations proved to be an effective tool in locating the positions of the H atoms reliably and verifying the salt configuration of the structure determined from powder data. Crystal packing analysis of these structures revealed that the loxapine succinate structure is based on chains of protonated loxapine molecules while the monohydrate contains dispersion stabilized centrosymmetric dimers. Incorporation of water molecules within the crystal lattice significantly alters the molecular packing and protonation state of the succinic acid.

scholarly journals Crystal structure, Hirshfeld surface analysis and computational study of 2-chloro-N-[4-(methylsulfanyl)phenyl]acetamide

2020 ◽  
Vol 76 (4) ◽  
pp. 594-598
Author(s):  
Sitthichok Mongkholkeaw ◽  
Apisit Songsasen ◽  
Tanwawan Duangthongyou ◽  
Kittipong Chainok ◽  
Songwut Suramitr ◽  
...  
Keyword(s):  
Surface Analysis ◽  
Title Compound ◽  
Crystal Packing ◽  
Computational Study ◽  
Dft Method ◽  
Hirshfeld Surface ◽  
Basis Set ◽  
Hirshfeld Surface Analysis ◽  
Compound C ◽  
Out Of Plane

In the title compound, C9H10ClNOS, the amide functional group –C(=O)NH– adopts a trans conformation with the four atoms nearly coplanar. This conformation promotes the formation of a C(4) hydrogen-bonded chain propagating along the [010] direction. The central part of the molecule, including the six-membered ring, the S and N atoms, is fairly planar (r.m.s. deviation of 0.014). The terminal methyl group and the C(=O)CH2 group are slightly deviating out-of-plane while the terminal Cl atom is almost in-plane. Hirshfeld surface analysis of the title compound suggests that the most significant contacts in the crystal are H...H, H...Cl/Cl...H, H...C/C...H, H...O/O...H and H...S/S...H. π–π interactions between inversion-related molecules also contribute to the crystal packing. DFT calculations have been performed to optimize the structure of the title compound using the CAM-B3LYP functional and the 6–311 G(d,p) basis set. The theoretical absorption spectrum of the title compound was calculated using the TD–DFT method. The analysis of frontier orbitals revealed that the π–π* electronic transition was the major contributor to the absorption peak in the electronic spectrum.

Synthesis of [Re2Cl4(O)2(µ-O)(3,5-lut)4] and investigation of its structure via X-ray and spectroscopic measurements and DFT calculations

2014 ◽  
Vol 68 (5) ◽  
Author(s):  
Sławomir Michalik ◽  
Jan Małecki ◽  
Natalia Młynarczyk
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Computational Study ◽  
Dft Method ◽  
Time Dependent ◽  
Electronic Transitions ◽  
X Ray Diffraction ◽  
Functional Theory ◽  
X Ray ◽  
The Density Functional Theory

AbstractA combined experimental and computational study of the dinuclear rhenium(V) complex containing (ReO)2(µ-O) core is presented in this article. The solid-state [Re2Cl4(O)2(µ-O)(3,5-lut)4] (3,5-lut = 3,5-dimethylpyridine) complex was characterised structurally (by single crystal X-ray diffraction) and spectroscopically (by IR, NMR, UV-VIS). The electronic structure was examined using the density functional theory (DFT) method. The spin-allowed electronic transitions were calculated using the time-dependent DFT method, and the UV-VIS spectrum was discussed.

scholarly journals Molecular and crystal structure, optical properties and DFT studies of 1,4-dimethoxy-2,5-bis[2-(4-nitrophenyl)ethenyl]benzene

2020 ◽  
Vol 76 (6) ◽  
pp. 940-943
Author(s):  
Georgii Bogdanov ◽  
Evgenii Oskolkov ◽  
Jenna Bustos ◽  
Viktor Glebov ◽  
John P. Tillotson ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Phenyl Ring ◽  
Crystal Packing ◽  
Dft Studies ◽  
X Ray Diffraction ◽  
X Ray ◽  
Vertical Excitation ◽  
Benzene Rings ◽  
Homo And Lumo ◽  
Title Molecule

The title compound DBNB, C24H20N2O6, has been crystallized and studied by X-ray diffraction, spectroscopic and computational methods. In the title molecule, which is based on a 1,4-distyryl-2,5-dimethoxybenzene core with p-nitro-substituted terminal benzene rings, the dihedral angle between mean planes of the central fragment and the terminal phenyl ring is 16.46 (6)°. The crystal packing is stabilized by π–π interactions. DFT calculations at the B3LYP/6–311 G(d,p) level of theory were used to compare the optimized structures with the experimental data. Energy parameters, including HOMO and LUMO energies, their difference, and vertical excitation and emission energies were obtained.

X-ray and DFT Investigation of (E)-4-bromo-5-methoxy-2-((o-tolylimino)methyl)phenol Compound

2018 ◽  
pp. 454-461
Keyword(s):  
Density Functional ◽  
Theoretical Calculations ◽  
Population Analysis ◽  
Diffraction Method ◽  
Dft Method ◽  
Basis Set ◽  
X Ray Diffraction ◽  
Mulliken Population ◽  
Charge Delocalization ◽  
X Ray

(E)-4-bromo-5-methoxy-2-((o-tolylimino)methyl)phenol was investigated by experimental and theoretical methodologies. The solid state molecular structure was determined by X-ray diffraction method. All theoretical calculations were performed by density functional theory (DFT) method by using B3LYP/6-31G(d,p) basis set. The titled compound showed the preference of enol form, as supported by X-ray diffraction method. The geometric and molecular properties were compaired for both enol-imine and keto-amine forms for title compound. Stability of the molecule arises from hyperconjugative interactions, charge delocalization and intramolecular hydrogen bond has been analyzed using natural bond orbital (NBO) analysis. Mulliken population method and natural population analysis (NPA) have been studied. Also, condensed Fukui function and relative nucleophilicity indices calculated from charges obtained with orbital charge calculation methods (NPA). Molecular electrostatic potential (MEP) and non linear optical (NLO) properties are also examined.

Isoelectronic Trap Like Luminescence Centers Of Ingan

1997 ◽  
Vol 482 ◽  
Author(s):  
H. Kanie ◽  
H. Koami ◽  
T. Kawano ◽  
T. Totsuka
Keyword(s):  
Luminescence Center ◽  
Energy Levels ◽  
Diffraction Method ◽  
Localized States ◽  
X Ray Diffraction ◽  
X Ray ◽  
Luminescence Centers ◽  
Microscopic Inhomogeneity ◽  
Broad Emission ◽  
Stokes Shifts

AbstractThis paper describes the characteristics of the luminescence centers observed in the various photoluminescence (PL) and photoluminescence excitation (PLE) spectra of hexagonal InxGa1−xN microcrystals, synthesized by the nitridation of sulfide in the In concentration range of 2%<x<6%. The grown crystals showed macroscopic and microscopic inhomogeneity. A series of component bands expressed by Gaussian functions with discrete peak energies selected from the frequently observed peaks in the PL spectra and full width at half maximum obtained from the narrowest PL bands were fitted well to observed broad emission bands. As some of the peak energies of the component bands coincide with those of the bands that are attributed to the decay of excitons at the localized states caused by the In content fluctuation in the literature, we concluded the luminescence center for the component bands also originates from the fluctuation of the In contents. Although the In contents of the samples determined by the X ray diffraction method were compatible the gap energies from the PLE measurements were different. The PLE spectra showed that the Stokes shifts were large and the gap energies were irrelevant to the emission band peaks. The excitation bands for the emission bands in the range of 2.8 to 2.48 eV were located at 3.36, 3.26, and 3.21 eV. These results indicate that the states of the luminescence center are localized and the energy levels are discrete. To obtain the microscopic structure of the localized states in InxGa1−xN, we propose the isoelectronic atom cluster model comparable with Te clusters in ZnSeTe.

Die Photoreaktion von Re2(CO)10 mit Ethylen und Ethylenderivaten/ The Photoreaction of Re2(CO)10 with Ethylene and Ethylene Derivatives

1986 ◽  
Vol 41 (7) ◽  
pp. 904-914 ◽  
Author(s):  
Cornelius G. Kreiter ◽  
Karl Heinz Franzreb ◽  
William S. Sheldrick
Keyword(s):  
Crystal Structure ◽  
Structure Analysis ◽  
Molecular And Crystal Structure ◽  
Reaction Products ◽  
X Ray ◽  
Dirhenium Complexes ◽  
Elemental Analyses ◽  
Reduced Temperature

AbstractRe2(CO)10 (1) has been photolyzed at reduced temperature in the presence of ethylene (2), styrene (3) or 2-methyl-1,3-butadiene (4), respectively. Main products of these reactions are the octacarbonyl-μ-hydrido-μ-η2:1-olefinyl-dirhenium (6, 9, 12, 13, 15) and tridecacarbonyl-μ-η2:1- olefinyl-trirhenium complexes (7, 14, 16). In lesser amounts, three isomeric undecacarbonyl-μ- hydrido-bis(μ-η2:1-vinyl)trirhenium com pounds (8 a, 8 b, 8 c), enneacarbonyl-η2-ethylenedirhenium (5) and three octacarbonyl-η4-diene-dirhenium complexes (10,17,18) are formed. The reaction products were separated by HPL chromatography. They were characterized by IR and NM R spectroscopy (1H , 13C) and by C, H elemental analyses. The molecular and crystal structure of tridecacarbonyl-η2:1-E-3-methyl-1,3-butadien-1-yl-trirhenium was determined by X-ray structure analysis.

scholarly journals Theoretical Studies of Electronic Structure and Photophysical Properties of a Series of Indoline Dyes with Triphenylamine Ligand

2015 ◽  
Vol 2015 ◽  
pp. 1-9 ◽  
Author(s):  
Xue-Feng Ren ◽  
Jun Zhang ◽  
Guo-Jun Kang
Keyword(s):  
Density Functional ◽  
Energy Gap ◽  
Photophysical Properties ◽  
Energy Levels ◽  
Dye Sensitized Solar Cells ◽  
Dft Method ◽  
Structure Property ◽  
Lumo Energy ◽  
Semiconductor Interface ◽  
Homo And Lumo

To design efficient organic sensitizer, a series of D-π-A indoline dyes with different donor parts have been investigated by density functional theory (DFT) and time-dependent DFT (TD-DFT) approach. The molecular geometries, frontier molecular orbitals, and absorption spectra of these dyes have been systematically investigated to provide comprehensive understanding of the structure-property relationships. Compared with D149, our designed dyes have proper HOMO and LUMO energy level, narrowed HOMO-LUMO energy gap, and broadened absorption band by introducing the N(CH3)2and N(phenyl)2groups at the donor part. Furthermore, the dimeric dyes and dye-(TiO2)6systems have been optimized by DFT method to simulate the intermolecular interactions, as well as interaction between the dyes dimmers and semiconductor interface, respectively. Through the analyses of absorption energies (Eads), energy levels of the HOMO and LUMO, light harvesting efficiency (LHE), and the driving force of electrons injections (ΔGinject), it is found that the designed dyes should have improved optical properties by importing the N(CH3)2group. This work is hoped to provide a theoretical guiding role in design of new dyes for dye-sensitized solar cells.

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