Unsymmetrical phthalocyanines containing azo moiety; Synthesis and photophysical properties

2019 ◽  
Vol 23 (11n12) ◽  
pp. 1563-1569 ◽  
Author(s):  
Ebru Özkan Garip ◽  
Mukaddes Özçeşmeci ◽  
Ramazan Katırcı ◽  
İbrahim Özçeşmeci ◽  
Esin Hamuryudan
Keyword(s):  
Density Functional ◽  
Photophysical Properties ◽  
Energy Difference ◽  
Proton Nuclear Magnetic Resonance ◽  
Visible Spectroscopy ◽  
Lumo Energy ◽  
Functional Theory ◽  
Metal Free ◽  
Aggregation Behaviors ◽  
Homo Lumo

Unsymmetrical metal-free phthalocyanine was synthesized through cyclotetramerization of 4-[2,6-dimethyl-4-(4-tert-butyl-phenylazo)phenoxy]phthalonitrile and 4-(hexylthio)phthalonitrile in the presence of lithium in [Formula: see text]-pentanol, then metal-free phthalocyanine was obtained by acidification with acetic acid. Finally, metalation was achieved by refluxing metal-free phthalocyanine in [Formula: see text]-pentanol in the presence of zinc (II) salt. The structure of synthesized phthalocyanine derivatives were characterized by using proton nuclear magnetic resonance, mass spectrometry, ultraviolet–visible spectroscopy, and Fourier transform infrared spectroscopy. The HOMO–LUMO energies were computed using density functional theory. The HOMO–LUMO energy difference is 2.28 eV. The calculated results were consistent with the experimental data. In addition, aggregation behaviors and general trends for photophysical properties of these phthalocyanine derivatives were studied in tetrahydrofuran. The emission intensities of these phthalocyanine derivatives were strongly quenched by 1,4-benzoquinone in tetrahydrofuran.

Saturated N,X-Heterocyclic Carbenes (X=N, O, S, P, Si, C, and B): Stability, Nucleophilicity, and Basicity

2015 ◽  
Vol 68 (9) ◽  
pp. 1438 ◽  
Author(s):  
Zahra Azizi ◽  
Mehdi Ghambarian ◽  
Mohammad A. Rezaei ◽  
Mohammad Ghashghaee
Keyword(s):  
Density Functional ◽  
Energy Gap ◽  
Energy Difference ◽  
Heterocyclic Carbenes ◽  
Structure Stability ◽  
Triplet Energy ◽  
Lumo Energy ◽  
Dft Methods ◽  
Functional Theory ◽  
Homo Lumo

Various saturated five-membered N,X-heterocyclic carbenes (X = N, O, S, P, Si, C, and B) have been studied by ab initio and density functional theory (DFT) methods. The substitutions alter the properties of the reference carbene from the viewpoint of electronic structure, stability, nucleophilicity, and basicity. Our study shows that the oxygen containing carbene (X = O) induces the highest HOMO–LUMO energy gap (ΔEHOMO–LUMO), while carbene with X = N has the widest singlet–triplet energy difference (ΔEs–t). The nucleophilicity of the carbene derivatives increased upon replacement of C, Si, and B, with the effect of the boron substituent being more pronounced. In addition, the basicity of the structure increased for the carbene derivatives with X = C and B with the latter substitution imposing a remarkably higher effect. Moreover, the substitution of boron at the α-position of the carbene increased the nucleophilicity and basicity, while inducing a reduction in the values of ΔEs–t and ΔEHOMO–LUMO.

STRUCTURES, ABSORPTION SPECTRA, AND ELECTRONIC PROPERTIES OF POLYFLUORENE AND ITS DERIVATIVES: A THEORETICAL STUDY

2006 ◽  
Vol 05 (03) ◽  
pp. 595-608 ◽  
Author(s):  
KRIENGSAK SRIWICHITKAMOL ◽  
SONGWUT SURAMITR ◽  
POTJAMAN POOLMEE ◽  
SUPA HANNONGBUA
Keyword(s):  
Density Functional Theory ◽  
Density Functional ◽  
Energy Gap ◽  
Level Energy ◽  
Excitation Energies ◽  
Lumo Energy ◽  
Functional Theory ◽  
Local Energy Minimum ◽  
Pi Systems ◽  
Homo Lumo

The structural and energetic properties of polyfluorene and its derivatives were investigated, using quantum chemical calculations. Conformational analysis of bifluorene was performed by using ab initio (HF/6-31G* and MP2/6-31G*) and density functional theory (B3LYP/6-31G*) calculations. The results showed that the local energy minimum of bifluorene lies between the coplanar and perpendicular conformation, and the B3LYP/6-31G* calculations led to the overestimation of the stability of the planar pi systems. The HOMO-LUMO energy differences of fluorene oligomers and its derivatives — 9,9-dihexylfluorene (DHPF), 9,9-dioctylfluorene (PFO), and bis(2-ethylhexyl)fluorene (BEHPF) — were calculated at the B3LYP/6-31G* level. Energy gaps and effective conjugation lengths of the corresponding polymers were obtained by extrapolating HOMO-LUMO energy differences and the lowest excitation energies to infinite chain length. The lowest excitation energies and the maximum absorption wavelength of polyfluorene were also performed, employing the time-dependent density functional theory (TDDFT) and ZINDO methods. The extrapolations, based on TDDFT and ZINDO calculations, agree well with experimental results. These theoretical methods can be useful for the design of new polymeric structures with a reducing energy gap.

SOLVENT EFFECTS ON THE ELECTRONIC STRUCTURE AND NON-LINEAR OPTICAL PROPERTIES OF PYRENE AND SOME OF ITS DERIVATIVES BASED ON DENSITY FUNCTIONAL THEORY

2021 ◽  
Vol 4 (4) ◽  
pp. 236-251
Author(s):  
A. S. Gidado ◽  
L. S. Taura ◽  
A. Musa
Keyword(s):  
Density Functional Theory ◽  
Gas Phase ◽  
Density Functional ◽  
Energy Gap ◽  
Chemical Reactivity ◽  
Basis Set ◽  
Lumo Energy ◽  
Functional Theory ◽  
Organic Optoelectronic ◽  
Homo Lumo

Pyrene (C16H10) is an organic semiconductor which has wide applications in the field of organic electronics suitable for the development of organic light emitting diodes (OLED) and organic photovoltaic cells (OPV). In this work, Density Functional Theory (DFT) using Becke’s three and Lee Yang Parr (B3LYP) functional with basis set 6-311++G(d, p) implemented in Gaussian 03 package was  used to compute total energy, bond parameters, HOMO-LUMO energy gap, electron affinity, ionization potential, chemical reactivity descriptors, dipole moment, isotropic polarizability (α), anisotropy of polarizability ( Δ∝) total first order hyper-polarizability () and second order hyperpolarizability (). The molecules used are pyrene, 1-chloropyrene and 4-chloropyrene  in gas phase and in five different solvents: benzene, chloroform, acetone, DMSO and water. The results obtained show that solvents and chlorination actually influenced the properties of the molecules. The isolated pyrene in acetone has the largest value of HOMO-LUMO energy gap of and is a bit closer to a previously reported experimental value of  and hence is the most stable. Thus, the pyrene molecule has more kinetic stability and can be described as low reactive molecule. The calculated dipole moments are in the order of 4-chloropyrene (1.7645 D) < 1-chloropyrene (1.9663 D) in gas phase. The anisotropy of polarizability ( for pyrene and its derivatives were found to increase with increasing polarity of the solvents.  In a nutshell, the molecules will be promising for organic optoelectronic devices based on their computed properties as reported by this work.

Meso-alkynyl corroles and their cobalt(III), manganese(III) and gallium(III) complexes

2020 ◽  
Vol 24 (05n07) ◽  
pp. 737-749
Author(s):  
Michael Haas ◽  
Sabrina Gonglach ◽  
Wolfgang Schöfberger
Keyword(s):  
Density Functional Theory ◽  
Electronic Structure ◽  
Density Functional ◽  
Theoretical Study ◽  
Lumo Energy ◽  
Functional Theory ◽  
Energy Gaps ◽  
Peak Broadening ◽  
Homo And Lumo ◽  
Homo Lumo

We report routes towards synthesis of novel [Formula: see text]-conjugated freebase cobalt, copper, gallium and manganese meso-alkynylcorroles. UV-vis spectra show that extensive peak broadening, red shifts, and changes in the oscillator strength of absorptions increase with the extension of [Formula: see text]-conjugation. Using density functional theory (DFT), we have carried out a first theoretical study of the electronic structure of these metallocorroles. Decreased energy gaps of about 0.3–0.4 eV between the HOMO and LUMO orbitals compared to the corresponding copper, gallium and manganese meso-5,10,15 triphenylcorrole are observed. In all cases, the HOMO energies are nearly unperturbed as the [Formula: see text]-conjugation is expanded. The contraction of the HOMO–LUMO energy gaps is attributed to the lowered LUMO energies.

scholarly journals Crystal structure, Hirshfeld surface analysis and DFT study of N-(2-amino-5-methylphenyl)-2-(5-methyl-1H-pyrazol-3-yl)acetamide

2021 ◽  
Vol 77 (6) ◽  
pp. 638-642
Author(s):  
Gamal Al Ati ◽  
Karim Chkirate ◽  
Joel T. Mague ◽  
Nadeem Abad ◽  
Redouane Achour ◽  
...  
Keyword(s):  
Surface Analysis ◽  
Density Functional ◽  
Energy Gap ◽  
Crystal Packing ◽  
Layer Structure ◽  
Hirshfeld Surface ◽  
Hirshfeld Surface Analysis ◽  
Lumo Energy ◽  
Functional Theory ◽  
Homo Lumo

The title molecule, C13H16N4O, adopts an angular conformation. In the crystal a layer structure is generated by N—H...O and N—H...N hydrogen bonds together with C—H...π(ring) interactions. Hirshfeld surface analysis indicates that the most important contributions to the crystal packing are from H...H (53.8%), H...C/C...H (21.7%), H...N/N...H (13.6%), and H...O/O...H (10.8%) interactions. The optimized structure calculated using density functional theory (DFT) at the B3LYP/ 6–311 G(d,p) level is compared with the experimentally determined structure in the solid state. The calculated HOMO–LUMO energy gap is 5.0452 eV.

scholarly journals Crystal structure and DFT study of a zinc xanthate complex

2019 ◽  
Vol 75 (11) ◽  
pp. 1582-1585 ◽  
Author(s):  
Adnan M. Qadir ◽  
Sevgi Kansiz ◽  
Necmi Dege ◽  
Georgina M. Rosair ◽  
Igor O. Fritsky
Keyword(s):  
Molecular Structure ◽  
Electrostatic Potential ◽  
Density Functional ◽  
Molecular Electrostatic Potential ◽  
Energy Gap ◽  
Three Dimensional ◽  
Intramolecular Interactions ◽  
Lumo Energy ◽  
Functional Theory ◽  
Homo Lumo

In the title compound, bis(2-methoxyethyl xanthato-κS)(N,N,N′,N′-tetramethylethylenediamine-κ2 N,N′)zinc(II) acetone hemisolvate, [Zn(C4H7O2S2)2(C6H16N2)]·0.5C3H6O, the ZnII ion is coordinated by two N atoms of the N,N,N′,N′-tetramethylethylenediamine ligand and two S atoms from two 2-methoxyethyl xanthate ligands. The amine ligand is disordered over two orientations and was modelled with refined occupancies of 0.538 (6) and 0.462 (6). The molecular structure features two C—H...O and two C—H...S intramolecular interactions. In the crystal, molecules are linked by weak C—H...O and C—H...S hydrogen bonds, forming a three-dimensional supramolecular architecture. The molecular structure was optimized using density functional theory (DFT) at the B3LYP/6–311 G(d,p) level. The smallest HOMO–LUMO energy gap (3.19 eV) indicates the suitability of this crystal for optoelectronic applications. The molecular electrostatic potential (MEP) further identifies the positive, negative and neutral electrostatic potential regions of the molecules. Half a molecule of disordered acetone was removed with the solvent-mask procedure in OLEX2 [Dolomanov et al. (2009). J. Appl. Cryst. 42, 339–341] and this contribition is included in the formula.

scholarly journals Investigation of the Effects of Solvents on the Structural, Electronic and Thermodynamic Properties of Rosiglitazone Based on Density Functional Theory

2019 ◽  
pp. 1-18
Author(s):  
R. A. Ismail ◽  
A. B. Suleiman ◽  
A. S. Gidado ◽  
A. Lawan ◽  
A. Musa
Keyword(s):  
Density Functional Theory ◽  
Dipole Moment ◽  
Thermodynamic Properties ◽  
Gas Phase ◽  
Density Functional ◽  
Dielectric Constants ◽  
Basis Sets ◽  
Lumo Energy ◽  
Functional Theory ◽  
Homo Lumo

Rosiglitazone ( C18H19N3O3S ) is an anti-diabetic drug that reduces insulin resistance in patients with type 2 diabetes. The parameters (bond lengths and bond angles), HOMO, LUMO, HOMO-LUMO energy gap, dipole moment, thermodynamic properties, total energy and vibrational frequencies and intensities of the Rosiglitazone molecule in gas phase and in solvents (Water, Ethanol, DMSO and Acetonitrile) were calculated based on Density Functional Theory (DFT) using standard basis sets: B3LYP/6-31G(d,p), B3LYP/6-31+G(d,p) and B3LYP/6-31++G(d,p). Windows version of Gaussian 09 was used for all the calculations. From the results obtained, the solvents have little influence on the optimized parameters of the molecule. The highest HOMO value of -5.433 eV was found in gas phase showing that the molecule will best donate electron in the gas phase, followed by ethanol in comparison with other solvents. The values of the HOMO were observed to increase with the decrease in dielectric constants of the solvents across all the basis sets used. The lowest LUMO energy of -1.448 eV was found to be in ethanol which shows that the molecule will best accept electron in ethanol compared to the gas phase and other solvents. The largest HOMO-LUMO gap of 4.285 eV was found in water which shows its higher kinetic stability and less chemical reactivity compared to other solvents and in the gas phase. The chemical softness of the molecule was found to decrease as the dielectric constants of the solvents increased namely from ethanol to water. The chemical hardness was found to slightly increase with the increase in dielectric constants of the solvents. The highest value of the dipole moment of 4.6874 D was found in water indicating that the molecule will have the strongest intermolecular interactions in water compared to other solvents and in the gas phase. The total energy increased as the dielectric constants of the solvents decreased from water to ethanol. The vibrational frequencies and intensities increased as the dielectric constants of the solvents increased from ethanol to water. The results confirmed the effects of solvents on the structural, electronic and thermodynamic properties of the studied molecule and will be useful in the design and development of rosiglitazone as an anti-diabetic drug.

scholarly journals Structure, electronic and optical properties of chalcopyrite-type nano-clusters XFeY2 (X=Cu, Ag, Au; Y=S, Se, Te): a density functional theory study

2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Prabhat Ranjan ◽  
Praveen K. Surolia ◽  
Tanmoy Chakraborty
Keyword(s):  
Density Functional Theory ◽  
Dielectric Constant ◽  
Refractive Index ◽  
Optical Properties ◽  
Solar Cells ◽  
Density Functional ◽  
Energy Gap ◽  
Lumo Energy ◽  
Functional Theory ◽  
Homo Lumo

Abstract Iron-based chalcopyrite materials have diverse applications in solar cells, spintronic, thermoelectric devices, LEDs and medical sciences. In this report we have studied structure, electronic and optical properties of chalcopyrite-type nano-cluster XFeY2 (X=Cu, Ag, Au; Y=S, Se, Te) systematically by using Density Functional Theory (DFT). Our computed HOMO-LUMO energy gap of XFeY2 is in the range of 1.568–3.982 eV, which endorses its potential application in optoelectronic devices and solar cells. The result shows that chalcopyrite-type material AuFeS2 having a star-type structure with point group C2v and sextet spin multiplicity, is the most stable cluster with HOMO-LUMO energy gap of 3.982 eV. The optical properties viz. optical electronegativity, refractive index, dielectric constant, IR and Raman activity of these nano-clusters are also investigated. The result exhibits that HOMO-LUMO energy gap of XFeY2 along with optical electronegativity and vibrational frequency decreases from S to Se to Te, whereas refractive index and dielectric constant increases in the reverse order.

scholarly journals Synthesis and investigation on optical and electrochemical properties of 2,4-diaryl-9-chloro-5,6,7,8-tetrahydroacridines

2021 ◽  
Vol 17 ◽  
pp. 2450-2461
Author(s):  
Najeh Tka ◽  
Mohamed Adnene Hadj Ayed ◽  
Mourad Ben Braiek ◽  
Mahjoub Jabli ◽  
Peter Langer
Keyword(s):  
Density Functional Theory ◽  
Cyclic Voltammetry ◽  
Density Functional ◽  
Energy Levels ◽  
Cross Coupling ◽  
Density Functional Theory Calculations ◽  
Facile Synthesis ◽  
Lumo Energy ◽  
Functional Theory ◽  
Homo Lumo

A facile synthesis of 2,4-diaryl-9-chloro-5,6,7,8-tetrahydroacridine derivatives is reported which is based on POCl3-mediated cyclodehydration followed by double Suzuki–Miyaura cross-coupling. The absorption and fluorescence properties of the obtained products were investigated and their HOMO/LUMO energy levels were estimated by cyclic voltammetry measurements. Besides, density functional theory calculations were carried out for further exploration of their electronic properties.

scholarly journals Synthesis, DFT calculations, photophysical, photochemical properties of peripherally metallophthalocyanines bearing (2-(benzo[d] [1,3] dioxol-5-ylmethoxy) phenoxy) substituents

2021 ◽  
Author(s):  
Derya Güngördü Solğun ◽  
Ümit Yıldıko ◽  
Mehmet Salih Ağırtaş
Keyword(s):  
Dft Calculations ◽  
Density Functional ◽  
Fluorescence Emission ◽  
Docking Studies ◽  
Lumo Energy ◽  
Functional Theory ◽  
The Density Functional Theory ◽  
Homo Lumo ◽  
Electronic Surface ◽  
Absorption Measurements

Abstract 4-(2-(benzo[d] [1, 3] dioxol-5-ylmethoxy) phenoxy) phthalonitrile was first prepared as a starting material. Then, this new phthalonitrile derivative was reacted with Zn and Co salts to obtain new phthalocyanine complexes. Phthalocyanine complexes were evaluated by fluorescence emission, extinction, and absorption measurements. Aggregation studies show the compliance with the lambert-beer law in the concentration range studied for peripheral phthalocyanine compounds. The density functional theory (DFT) calculations of the metallophthalocyanines compounds were performed using B3LYP / 6-31G in Zn-Pc and B3LYP / LanL2DZ in Co-Pc to derive structural optimization, HOMO-LUMO energy parameters, and NLO properties. The calculated values of M-Pcs with different center atoms were obtained close to each other. Molecular electronic surface (MEP) maps of the studied compounds are mapped and discussed. The HOMO-LUMO energy gaps of our compounds studied are around 2.1 eV. The docking studies were performed with the phthalonitrile.

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