Synthesis and Optical Characterization of Mixed Ligands Beryllium Complexes for Display Device Applications

Synthesis and photoluminescent behaviour of mixed ligand based beryllium complexes with 2-(2-hydroxyphenyl)benzoxazole (HPB) and 5-chloro-8-hydroxyquinoline (Clq) or 5,7-dichloro-8-hydroxyquinoline (Cl2q) or 2-methyl-8-hydroxyquinoline (Meq) or 8-hydroxyquinoline (q) are reported in this work. These complexes, that is, [BeHPB(Clq)], [BeHPB(Cl2q)], [BeHPB(Meq)], and [BeHPB(q)], were prepared and their structures were confirmed by elemental analysis, Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and thermal analysis. The beryllium complexes exhibited good thermal stability up to ~300°C temperature. The photophysical properties of beryllium complexes were studied using ultraviolet-visible absorption and photoluminescence emission spectroscopy. The complexes showed absorption peaks due toπ-π∗andn-π∗electronic transitions. The complexes emitted greenish blue light with peak wavelength at 496 nm, 510 nm, 490 nm, and 505 nm, respectively, consisting of high intensity. Color tuning was observed with changing the substituents in quinoline ring ligand in metal complexes. The emitted light had Commission Internationale d’Eclairage color coordinates values atx=0.15andy=0.43for [BeHPB(Clq)],x=0.21andy=0.56for [BeHPB(Cl2q)],x=0.14andy=0.38for [BeHPB(Meq)],x=0.17andy=0.41for [BeHPB(q)]. Theoretical calculations using DFT/B3LYP/6-31G(d,p) method were performed to reveal the three-dimensional geometries and the frontier molecular orbital energy levels of these synthesized metal complexes.

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Push-Pull Chromophores Based on the Naphthalene Scaffold: Potential Candidates for Optoelectronic Applications

Materials ◽

10.3390/ma12081342 ◽

2019 ◽

Vol 12 (8) ◽

pp. 1342 ◽

Cited By ~ 11

Author(s):

Corentin Pigot ◽

Guillaume Noirbent ◽

Thanh-Tuân Bui ◽

Sébastien Péralta ◽

Didier Gigmes ◽

...

Keyword(s):

Theoretical Calculations ◽

Charge Transfer Band ◽

Photophysical Properties ◽

Polar Solvents ◽

Visible Absorption ◽

Synthetic Procedure ◽

Multistep Procedure ◽

Uv Visible ◽

Electron Withdrawing Group ◽

Positive Solvatochromism

A series of ten push-pull chromophores comprising 1H-cyclopenta[b]naphthalene-1,3(2H)-dione as the electron-withdrawing group have been designed, synthesized, and characterized by UV-visible absorption and fluorescence spectroscopy, cyclic voltammetry and theoretical calculations. The solvatochromic behavior of the different dyes has been examined in 23 solvents and a positive solvatochromism has been found for all dyes using the Kamlet-Taft solvatochromic relationship, demonstrating the polar form to be stabilized in polar solvents. To establish the interest of this polyaromatic electron acceptor only synthesizable in a multistep procedure, a comparison with the analog series based on the benchmark indane-1,3-dione (1H-indene-1,3(2H)-dione) has been done. A significant red-shift of the intramolecular charge transfer band has been found for all dyes, at a comparable electron-donating group. Parallel to the examination of the photophysical properties of the different chromophores, a major improvement of the synthetic procedure giving access to 1H-cyclopenta[b]naphthalene-1,3(2H)-dione has been achieved.

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Influence of Electronic Environment on the Radiative Efficiency of 9-Phenyl-9H-carbazole-Based ortho-Carboranyl Luminophores

Molecules ◽

10.3390/molecules26061763 ◽

2021 ◽

Vol 26 (6) ◽

pp. 1763

Author(s):

Seok Ho Lee ◽

Ji Hye Lee ◽

Min Sik Mun ◽

Sanghee Yi ◽

Eunji Yoo ◽

...

Keyword(s):

Radiative Decay ◽

Theoretical Calculations ◽

Photophysical Properties ◽

Phenyl Group ◽

Molecular Structures ◽

Quantum Yields ◽

Resonance Spectroscopy ◽

Electronic Environment ◽

Donor Acceptor ◽

Carbazole Group

The photophysical properties of closo-ortho-carboranyl-based donor–acceptor dyads are known to be affected by the electronic environment of the carborane cage but the influence of the electronic environment of the donor moiety remains unclear. Herein, four 9-phenyl-9H-carbazole-based closo-ortho-carboranyl compounds (1F, 2P, 3M, and 4T), in which an o-carborane cage was appended at the C3-position of a 9-phenyl-9H-carbazole moiety bearing various functional groups, were synthesized and fully characterized using multinuclear nuclear magnetic resonance spectroscopy and elemental analysis. Furthermore, the solid-state molecular structures of 1F and 4T were determined by X-ray diffraction crystallography. For all the compounds, the lowest-energy absorption band exhibited a tail extending to 350 nm, attributable to the spin-allowed π–π* transition of the 9-phenyl-9H-carbazole moiety and weak intramolecular charge transfer (ICT) between the o-carborane and the carbazole group. These compounds showed intense yellowish emission (λem = ~540 nm) in rigid states (in tetrahydrofuran (THF) at 77 K and in films), whereas considerably weak emission was observed in THF at 298 K. Theoretical calculations on the first excited states (S1) of the compounds suggested that the strong emission bands can be assigned to the ICT transition involving the o-carborane. Furthermore, photoluminescence experiments in THF‒water mixtures demonstrated that aggregation-induced emission was responsible for the emission in rigid states. Intriguingly, the quantum yields and radiative decay constants in the film state were gradually enhanced with the increasing electron-donating ability of the substituent on the 9-phenyl group (‒F for 1F < ‒H for 2P < ‒CH3 for 3M < ‒C(CH3)3 for 4T). These features indicate that the ICT-based radiative decay process in rigid states is affected by the electronic environment of the 9-phenyl-9H-carbazole group. Consequently, the efficient ICT-based radiative decay of o-carboranyl compounds can be achieved by appending the o-carborane cage with electron-rich aromatic systems.

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Theoretical Framework of 1,3-Thiazolium-5-Thiolates Mesoionic Compounds: Exploring the Nature of Photophysical Properties and Molecular Nonlinearity

10.26434/chemrxiv.12063261 ◽

2020 ◽

Author(s):

Zeyu Liu ◽

Shugui Hua ◽

Tian Lu ◽

Ziqi Tian

Keyword(s):

Optical Properties ◽

Rational Design ◽

Rayleigh Scattering ◽

Function Analysis ◽

Theoretical Calculations ◽

Photophysical Properties ◽

Optical Nonlinearity ◽

Nonlinear Properties ◽

Photoelectric Performance ◽

Wave Function Analysis

Inspired by a previous experimental study on the first-order hyperpolarizabilities of 1,3-thiazolium-5-thiolates mesoionic compounds using Hyper-Rayleigh scattering technique, we theoretically investigated the UV-Vis absorption spectra and every order polarizabilities of these mesoionic molecules. Based on the fact that the photophysical and nonlinear properties observed in the experiment can be perfectly replicated, our theoretical calculations explored the essential characteristics of the optical properties of the mesoionic compounds with different electron-donating groups at the level of electronic structures through various wave function analysis methods. The influence of the electron-donating ability of the donor on the optical properties of the molecules and the contribution of the mesoionic ring moiety to their optical nonlinearity are clarified, which have not been reported by any research so far. This work will help people understand the nature of optical properties of mesoionic-based molecules and provide guidance for the rational design of molecules with excellent photoelectric performance in the future.

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Photophysical Properties of Protoporphyrin IX, Pyropheophorbide-a, and Photofrin® in Different Conditions

Pharmaceuticals ◽

10.3390/ph14020138 ◽

2021 ◽

Vol 14 (2) ◽

pp. 138

Author(s):

Bauyrzhan Myrzakhmetov ◽

Philippe Arnoux ◽

Serge Mordon ◽

Samir Acherar ◽

Irina Tsoy ◽

...

Keyword(s):

Singlet Oxygen ◽

Photophysical Properties ◽

Protoporphyrin Ix ◽

Fluorescence Emission ◽

Solvent Polarity ◽

Visible Absorption ◽

Light Dosimetry ◽

Time Resolved ◽

Pyropheophorbide A ◽

Influence Of Solvent

Photodynamic therapy (PDT) is an innovative treatment of malignant or diseased tissues. The effectiveness of PDT depends on light dosimetry, oxygen availability, and properties of the photosensitizer (PS). Depending on the medium, photophysical properties of the PS can change leading to increase or decrease in fluorescence emission and formation of reactive oxygen species (ROS) especially singlet oxygen (1O2). In this study, the influence of solvent polarity, viscosity, concentration, temperature, and pH medium on the photophysical properties of protoporphyrin IX, pyropheophorbide-a, and Photofrin® were investigated by UV-visible absorption, fluorescence emission, singlet oxygen emission, and time-resolved fluorescence spectroscopies.

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Theoretical investigation on tautomerism and NLO properties of Salicylideneaniline derivatives

Canadian Journal of Physics ◽

10.1139/cjp-2021-0175 ◽

2021 ◽

Author(s):

N. Daho ◽

N. Benhalima ◽

F. KHELFAOUI ◽

O. SADOUKI ◽

M. Elkeurti ◽

...

Keyword(s):

Optical Properties ◽

Density Functional ◽

Energy Gap ◽

Intramolecular Proton Transfer ◽

Basis Set ◽

Frontier Molecular Orbital ◽

Molecular Orbital Calculations ◽

Visible Absorption ◽

Charge Delocalization ◽

Intramolecular Hydrogen

In this work, a comprehensive investigation of the salicylideneaniline derivatives is carried out using density functional theory to determine their linear and non-linear optical properties. Geometry optimizations, for gas and solvent phases, of the tautomers (enol and keto forms) are calculated using B3LYP levels with 6–31G (d,p) basis set . An intramolecular proton transfer, for 1SA-E and 2SA-E, is performed by a PES scan process at the B3LYP/6-31G (d,p) level. The optical properties are determined and show that they have extremely high nonlinear optical properties. In addition, the RDG analysis, MEP, and gap energy are calculated. The low energy gap value indicates the possibility of intramolecular charge transfer. The frontier molecular orbital calculations clearly show the inverse relationship of HOMO–LUMO gap with the first-order hyperpolarizability (β = 59.6471 × 10-30 esu), confirming that the salicylideneaniline derivatives can be used as attractive future NLO materials. Therefore, the reactive sites are predicted using MEP and the visible absorption maxima are analyzed using a theoretical UV–Vis spectrum. Natural bond orbitals are used to investigate the stability, charge delocalization, and intramolecular hydrogen bond.

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Photophysical Properties of Transition Metal Complexes

Handbook of Photochemistry ◽

10.1201/9781420015195-8 ◽

2006 ◽

pp. 387-430

Keyword(s):

Transition Metal ◽

Metal Complexes ◽

Transition Metal Complexes ◽

Photophysical Properties

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QTAIM investigation of bis(pyrazol-1-yl)methane derivative and its Zn(II) complexes (ZnLX2, X=Cl, Br or I)

Journal of the Serbian Chemical Society ◽

10.2298/jsc150224027z ◽

2015 ◽

Vol 80 (8) ◽

pp. 997-1008 ◽

Cited By ~ 3

Author(s):

Maryam Dehestani ◽

Leila Zeidabadinejad

Keyword(s):

Molecular Orbital ◽

Critical Points ◽

Structural Parameters ◽

Frontier Molecular Orbital ◽

Orbital Energy ◽

Theory Approach ◽

Topological Parameters ◽

Molecular Orbital Energy ◽

Highest Occupied Molecular Orbital ◽

Lowest Unoccupied Molecular Orbital

Topological analyses of the electron density using the quantum theory of atoms in molecules (QTAIM) have been carried out at the B3PW91/6-31g (d) theoretical level, on bis(pyrazol-1-yl)methanes derivatives 9-(4-(di (1H-pyrazol-1-yl)-methyl)phenyl)-9H-carbazole (L) and its zinc(II) complexes: ZnLCl2 (1), ZnLBr2 (2) and ZnLI2 (3). The topological parameters derived from Bader theory were also analyzed; these are characteristics of Zn-bond critical points and also of ring critical points. The calculated structural parameters are the frontier molecular orbital energies highest occupied molecular orbital energy (EHOMO), lowest unoccupied molecular orbital energy (ELUMO), hardness (?), softness (S), the absolute electronegativity (?), the electrophilicity index (?) and the fractions of electrons transferred (?N) from ZnLX2 complexes to L. The numerous correlations and dependencies between energy terms of the Symmetry Adapted Perturbation Theory approach (SAPT), geometrical, topological and energetic parameters were detected and described.

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Theoretical Study of Solvent Effects on the Electronic and Thermodynamic Properties of Tetrathiafulvalene (TTF) Molecule Based on DFT

Asian Journal of Research and Reviews in Physics ◽

10.9734/ajr2p/2021/v5i230162 ◽

2021 ◽

pp. 42-54

Author(s):

Rabiu Nuhu Muhammad ◽

N. M. Mahraz ◽

A. S Gidado ◽

A. Musa

Keyword(s):

Thermodynamic Properties ◽

Bond Length ◽

Density Functional ◽

Theoretical Study ◽

Energy Gap ◽

Basis Set ◽

Basis Sets ◽

Frontier Molecular Orbital ◽

Orbital Energy ◽

Chemical Hardness

Tetrathiafulvalene () is an organosulfur compound used in the production of molecular devices such as switches, sensors, nonlinear optical devices and rectifiers. In this work, a theoretical study on the effects of solvent on TTF molecule was investigated and reported based on Density Functional Theory (DFT) as implemented in Gaussian 03 package using B3LYP/6-31++G(d,p) basis set. Different solvents were introduced as a bridge to investigate their effects on the electronic structure. The HUMO, LUMO, energy gap, global chemical index, thermodynamic properties, NLO and DOS analysis of the TTF molecule in order to determine the reactivity and stability of the molecule were obtained. The results obtained showed that the solvents have effects on the electronic and non-linear-optical properties of the molecule. The optimized bond length revealed that the molecule has strong bond in gas phase with smallest bond length of about 1.0834Å than in the rest of the solvents. It was observed that the molecule is more stable in acetonitrile with HOMO-LUMO gap and chemical hardness of 3.6373eV and 1.8187eV respectively. This indicates that the energy gap and chemical hardness of TTF molecule increases with the increase in polarity and dielectric constant of the solvents. The computed results agreed with the results in the literature. The thermodynamics and NLO properties calculation also indicated that TTF molecule has highest value of specific heat capacity (Cv), total dipole moment () and first order hyperpolarizability () in acetonitrile, while acetone has the highest value of entropy and toluene has a slightly higher value of zero point vibrational energy (ZPVE) than the rest of the solvents. The results show that careful selection of the solvents and basis sets can tune the frontier molecular orbital energy gap of the molecule and can be used for molecular device applications.

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