Recent Developments and Applications of Modern Density Functional Theory

Künne, L.

doi:10.1524/zpch.1998.204.part_1_2.263

Cited by 10 publications

(6 citation statements)

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“…The ground state geometries of all iridium complexes were optimized at the level of density functional theory (DFT) using Gaussian 09 software package . The excitation energies were calculated with linear response time-dependent DFT (TD-DFT) formalism. − A total of 60 excitations were calculated to reproduce the energy range of the experimental UV/vis absorption spectra. The spectra were generated using inhomogeneous Gaussian line-broadening of 0.08 eV to match with experimental absorption spectra.…”

Section: Methodsmentioning

confidence: 99%

“…Natural transition orbital (NTO) analysis was performed to obtain the hole–electron pairs that correspond to singlet excitation, , where a hole–electron transition from a ground state to an excited state could be realized through unitary transformation of transition density matrix of a specific excited state . For visualizing the lowest-energy emitting state, we plotted the dominant molecular orbitals by performing the eigenvector analysis on the lowest excited state.…”

Section: Methodsmentioning

confidence: 99%

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Heteroleptic Ir(III)N₆ Complexes with Long-Lived Triplet Excited States and in Vitro Photobiological Activities

Wang

Monro

Cui

et al. 2019

ACS Appl. Mater. Interfaces

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A series of cationic heteroleptic iridium(III) complexes bearing tris-diimine ligands [Ir(phen) 2 (Rphen)] 3+ (R-phen = phenanthroline (1), 3,8-diphenylphenanthroline (2), 3,8dipyrenylphenanthroline (3), 3-phenylphenanthroline (4), 3-pyrenylphenanthroline (5), and 3,8diphenylethynylphenanthroline (6)) were synthesized and characterized. These complexes possessed phen ligand-localized 1 π,π* transitions below 300 nm, and charge transfer ( 1 CT) and/or 1 π,π* transitions between 300 and 520 nm. In 1, 2, 4, and 6, the low-energy bands were mixed 1 CT/ 1 π,π*. However, the increased π-donating ability of the pyrenyl substituent(s) in 3 and 5 split the low-energy bands into a pyrene-based 1 π,π* transition at 300-380 nm and an intraligand charge transfer ( 1 ILCT) transition at 380-520 nm. All complexes were emissive at room temperature in CH 3 CN, but the parentage of the emitting state varied depending on the R substituent(s). Complex 1 exhibited predominantly phen ligand-localized 3 π,π* emission mixed with metal-to-ligand charge transfer ( 3 MLCT) character, while the emission of 2, 4, and 6 was predominantly from the excited-state with 3 π,π*/ 3 ILCT/ 3 MLCT character. The emission from 3 and 5 was dominated by pyrene-based 3 π,π* states mixed with 3 ILCT character. The different natures of the lowest triplet excited states were also reflected by the different spectral features and *

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Section: Methodsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Heteroleptic Ir(III)N₆ Complexes with Long-Lived Triplet Excited States and in Vitro Photobiological Activities

Wang

Monro

Cui

et al. 2019

ACS Appl. Mater. Interfaces

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“…The ideal octahedral geometries of complexes 1 – 11 were optimized in their singlet and triplet spin configurations by density functional theory (DFT) using the hybrid Perdew, Burke, and Ernzerhof functional (PBE1PBE) − and the LANL2DZ basis set − assigned for Ir and Br atoms and 6-31G* basis set − for all the remaining atoms. The absorption spectra were calculated using linear-response time dependent DFT (TDDFT) , by iteratively solving the eigenvalue equation using the Davidson algorithm. − For excited-state calculations, the density functional and basis sets were chosen being the same as those for the ground-state calculations. A total of 80 excited states were calculated with their corresponding transition energies and oscillator strengths.…”

Section: Experimental Sectionmentioning

confidence: 99%

Multifunctional Cationic Iridium(III) Complexes Bearing 2-Aryloxazolo[4,5-f][1,10]phenanthroline (N^N) Ligand: Synthesis, Crystal Structure, Photophysics, Mechanochromic/Vapochromic Effects, and Reverse Saturable Absorption

et al. 2017

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A series of 2-aryloxazolo[4,5-f][1,10]phenanthroline ligands (N^N ligands) and their cationic iridium(III) complexes (1-11, aryl = 4-NO-phenyl (1), 4-Br-phenyl (2), Ph (3), 4-NPh-phenyl (4), 4-NH-phenyl (5), pyridin-4-yl (6), naphthalen-1-yl (7), naphthalen-2-yl (8), phenanthren-9-yl (9), anthracen-9-yl (10), and pyren-1-yl (11)) were synthesized and characterized. By introducing different electron-donating or electron-withdrawing substituents at the 4-position of the 2-phenyl ring (1-5), or different aromatic substituents with varied degrees of π-conjugation (6-11) on oxazolo[4,5-f][1,10]phenanthroline ligand, we aim to understand the effects of terminal substituents at the N^N ligands on the photophysics of cationic Ir(III) complexes using both spectroscopic methods and quantum chemistry calculations. Complexes with the 4-R-phenyl substituents adopted an almost coplanar structure with the oxazolo[4,5-f][1,10]phenanthroline motif, while the polycyclic aryl substituents (except for naphthalen-2-yl) were twisted away from the oxazolo[4,5-f][1,10]phenanthroline motif. All complexes possessed strong absorption bands below 350 nm that emanated from the ligand-localized π,π*/ILCT (intraligand charge transfer) transitions, mixed with LLCT (ligand-to-ligand charge transfer)/MLCT (metal-to-ligand charge transfer) transitions. At the range of 350-570 nm, all complexes exhibited moderately strong ILCT/LLCT/MLCT transitions at 350-450 nm, and broad but very weak LLCT/MLCT absorption at 450-570 nm. Most of the complexes demonstrated moderate to strong room temperature phosphorescence both in solution and in the solid state. Among them, complex 7 also manifested a drastic mechanochromic and vapochromic luminescence effect. Except for complexes 1 and 4 that contain NO or NPh substituent at the phenyl ring, respectively, all other complexes exhibited moderate to strong triplet excited-state absorption in the spectral region of 440-750 nm. Moderate to very strong reverse saturable absorption (RSA) of these complexes appeared at 532 nm for 4.1 ns laser pulses. The RSA strength followed the trend of 7 > 11 > 9 > 3 > 2 ≈ 4 > 5 ≈ 10 ≈ 6 ≈ 8 > 1. The photophysical studies revealed that the different 2-aryl substituents on the oxazole ring impacted the singlet and triplet excited-state characteristics dramatically, which in turn notably influenced the RSA of these complexes.

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“…More negative electrostatic potential found near the CHO group is the main cause for electrophilic attack and also cause for C─H…O interactions with the neighborhood molecule. The difference between positive and negative potentials shows that the molecule is more polar [24,25] when compared to the vanillin and its polymorphs.…”

Section: Molecular Electrostatic Potential Analysismentioning

confidence: 99%

Facile Synthesis, Crystal Structure, Spectral Characterization, Quantum Chemical Calculations, and Hirshfeld Surface Analysis of 5‐Chloro‐3‐Methoxy‐4‐Hydroxybenzaldehyde

Nagapandiselvi¹

2021

Crystal Research and Technology

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This article deals with synthesis, growth, structure, and characterization of 5-chloro-3-methoxy-4-hydroxybenzaldehyde (5CMHBA or 5-chlorovanillin) single crystals. A facile one-pot method is employed for the chlorination of vanillin using N-chlorosuccinimide. After chlorination, the single crystals of 5CMHBA are grown by slow evaporation solution growth technique. Grown crystals are subjected to single crystal X-ray diffraction (SXRD), Fourier Transform Infrared (FTIR), and Thermogravimetric-Differential Thermal Analysis (TG-DTA). 5CMHBA crystallizes in the tetragonal crystal system with the space group P4 2 /n. Vibrational characteristics are studied using FTIR. Further, thermal studies of the crystal are carried out using simultaneous TG-DTA thermal analyzer. The molecular structure and its intermolecular interactions are studied by applying time-dependent density functional theory (TD-DFT) using Gaussian 09 program and Hirshfeld surface analysis. A lesser energy gap of the 5CMHBA compared to that of vanillin shows the high reactivity of the molecule. Dipole moment, polarizability, and hyper-polarizability are calculated in the molecular level and found to have greater polarizability than vanillin and also higher in order than that of standard urea molecule. This reveals the suitability of the molecule for nonlinear optical applications. The intermolecular interactions and porosity are analyzed and compared with vanillin and its polymorphs by Hirshfeld surface analysis.

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Recent Developments and Applications of Modern Density Functional Theory

Cited by 10 publications

References 0 publications

Heteroleptic Ir(III)N₆ Complexes with Long-Lived Triplet Excited States and in Vitro Photobiological Activities

Heteroleptic Ir(III)N₆ Complexes with Long-Lived Triplet Excited States and in Vitro Photobiological Activities

Multifunctional Cationic Iridium(III) Complexes Bearing 2-Aryloxazolo[4,5-f][1,10]phenanthroline (N^N) Ligand: Synthesis, Crystal Structure, Photophysics, Mechanochromic/Vapochromic Effects, and Reverse Saturable Absorption

Facile Synthesis, Crystal Structure, Spectral Characterization, Quantum Chemical Calculations, and Hirshfeld Surface Analysis of 5‐Chloro‐3‐Methoxy‐4‐Hydroxybenzaldehyde

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Recent Developments and Applications of Modern Density Functional Theory

Cited by 10 publications

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Heteroleptic Ir(III)N6 Complexes with Long-Lived Triplet Excited States and in Vitro Photobiological Activities

Heteroleptic Ir(III)N6 Complexes with Long-Lived Triplet Excited States and in Vitro Photobiological Activities

Multifunctional Cationic Iridium(III) Complexes Bearing 2-Aryloxazolo[4,5-f][1,10]phenanthroline (N^N) Ligand: Synthesis, Crystal Structure, Photophysics, Mechanochromic/Vapochromic Effects, and Reverse Saturable Absorption

Facile Synthesis, Crystal Structure, Spectral Characterization, Quantum Chemical Calculations, and Hirshfeld Surface Analysis of 5‐Chloro‐3‐Methoxy‐4‐Hydroxybenzaldehyde

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Heteroleptic Ir(III)N₆ Complexes with Long-Lived Triplet Excited States and in Vitro Photobiological Activities

Heteroleptic Ir(III)N₆ Complexes with Long-Lived Triplet Excited States and in Vitro Photobiological Activities