Theoretical design study on the electronic structure and photophysical properties of a series of osmium(II) complexes with different ancillary ligands

Han, Deming; Liu, Jian; Miao, Runzhong; Zhao, Lihui; Zhang, Gang

doi:10.1016/j.poly.2014.09.018

Cited by 11 publications

(4 citation statements)

References 33 publications

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“…All absorptions belong to SoS* or noS* transitions. The comparison of experimental and calculated values showed a good correlation for both compounds [ 23,24 ].…”

Section: T a B L Ementioning

confidence: 68%

Two Fluoro Compounds of Main Group Elements: Synthesis, Characterization, Theoretical and Spectroscopic Study

2015

JSC

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Two new compounds of fluorine: (C 2 H 5) 4 N[I 2 F] and (C 2 H 5) 4 N[Br 2 F] have been easily synthesized in a nearly quantitative by a direct reaction of (C 2 H 5) 4 NF, I 2 and Br 2. The products were isolated and characterized by elemental analysis and spectroscopic methods such as: Fourier transform infrared spectroscopy (FTIR) and ultraviolet-visible spectroscopy (UV-Vis). These compounds have been studied with the Scalar ZORA relativistic level of theory using the ADF program package. The molecular parameters, and vibrational spectra were calculated. The excitation energies were found by time-dependent perturbation density functional theory (TD-DFT). Molecule optimization, frequencies and excitation energies were calculated with standard Slatertype-orbital (STO) basis sets with triple-zeta quality double plus polarization functions (TZ2P) for all atoms. The FTIR, UV-Vis spectra and assignment of principal transitions and total density of state (TDOS) were extracted using the GaussSum 2.2 program. The comparison between experimental and calculated values shows that the experimental results correlate well with the predicted data.

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“…All absorptions belong to SoS* or noS* transitions. The comparison of experimental and calculated values showed a good correlation for both compounds [ 23,24 ].…”

Section: T a B L Ementioning

confidence: 68%

Two Fluoro Compounds of Main Group Elements: Synthesis, Characterization, Theoretical and Spectroscopic Study

2015

JSC

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“…The complexes C1 ‐ C10 show λ hole and λ electron values ranging from 0.19 to 0.46 eV and 0.29 to 0.40 eV, respectively (Figure ), which are comparable to those of neutral Pt(II) and Ir(III) complexes with O^O and N^O based ancillary ligands (λ hole ≈0.20‐0.50 eV and λ electron ≈0.20‐0.30 eV) . We take into account the Δλ=∣λ hole −λ electron ∣ as a measure of the λ hole and λ electron balance.…”

Section: Resultsmentioning

confidence: 91%

“…It has been determined that a large 3 MLCT contribution in the emissive state increases the k r and quantum yield Φ p as observed in Os, Ir, and Pt complexes The % 3 MLCT for a given excited state is obtained as the sum of the single 3 MLCT contributions from each monoexcitations from i to j orbitals:

%^{3} normalM normalL normalC normalT = {false\sum}_{I}^{n} ([]|, C_{I} (|, i \to j)) ([]|, {% (|, M)}_{i} - {% (|, M)}_{j})

where C I is the configuration coefficient of each monoexcitation from i to j orbital in the excited state wavefunction, and %( M ) i and %( M ) j are the metal contributions to the occupied i and virtual j orbitals, respectively (more details in Section S7 of the Supporting Information). The 3 MLCT contribution in C1 ‐ C3 is of 22%‐30%, which decreases in systems C4 ‐ C6 by the fluorination of the ppy ligand.…”

Section: Resultsmentioning

confidence: 99%

Insights into the luminescent properties of anionic cyclometalated iridium(III) complexes with ligands derived from natural products

Cortés‐Arriagada

Dreyse

Salas

et al. 2018

Int J of Quantum Chemistry

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In the search of remarkable anionic electroluminescent semiconductors to be applied in energy conversion devices such as Light Emitting Electrochemical Cells, we report the electronic, photophysical, and charge injection/transfer properties of a series of cyclometalated iridium(III) complexes through a DFT/TD-DFT procedure. The proposed semiconductors involve bidentated ligands based on natural products (salicylic acid and boldine), and phenylpyridine and phenylpyrazole as the cyclometalating units. The proposed compounds emit in the range of 446 to 571 nm, where the boldine based compounds have red-shifted emissions compared to their analogs with salicylic acid. Blue phosphors were obtained by the use of phenylpyrazole units; however, the ligand field is weak in these cases compared to the ligand field exerted by the phenylpyridine ligands. The latter allows the accessibility to the radiationless states for emitters below 495 nm as a result of the increased stability of the metal centered excited states; consequently, the luminescent quantum yield could be decreased. Conversely, the semiconductors with phenylpyridine units show a restricted accessibility to radiationless processes, which could result in emitters with a high luminescent quantum yield and low non-radiative constants. Finally, the proposed anionic semiconductors show a better balance between hole/electron transfer rate compared to related cationic Ir (III) complexes; while, the easier hole-electron injection is favored for semiconductors with salicylic acid and phenylpyridine units.anionic semiconductors, iridium complexes, LECs, luminescence, TD-DFTThe improvement of the lighting technologies is a challenge to reduce the consumption of electrical energy. Solid-state lighting (SSL) systems comprise LED (Light Emitting Diode), OLED (Organic Light Emitting Diode), and LEC (Light Emitting Electrochemical Cell) devices. [1,2] In particular, LECs consist of a layer of an ionic transition metal complex (iTMC) with luminescent properties, which is sandwiched between two electrodes; a cathode that consists of a metal layer, and a transparent conductive film that acts as the anode. [3][4][5] In addition, LECs require less stringent packaging procedures compared to OLEDs since the iTMC layers are processed from a solution, and also because the air-sensitive electron injection layers are not necessary. [3][4][5] The cationic Ir(III) cyclometalated complexes of general formula [Ir(C^N) 2 (N^N)] 1 (C^N: cyclometalating ligand and N^N: ancillary ligand) have been widely used as semiconductor iTMCs, due to their remarkable photophysical properties such as i) high ligand-field splitting energy; [6,7] ii) the strong spin-orbit coupling (SOC) exerted by Ir; [7,8] iii) and wider color tunability through chemical functionalization and its effects onto the energy of frontier molecular orbitals. [1,9] Despite the wide implementation of cationic Ir(III) complexes, anionic complexes have also emerged as semiconductors for use in LEC devices. [10][11][12] In this regard, t...

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“…The properties of the frontal molecular orbital (FMOs) have a significant effect on the excited states and electronic transitions of OLED materials. It is well known that the optical properties of the complexes are associated with FMOs especially, HOMO and LUMO [27].…”

Section: Molecular Orbital Propertiesmentioning

confidence: 99%

Effect of Substituents on Electronic Structure and Photophysical Properties of Re(I)(CO)<sub>3</sub>Cl(R-2, 2’-Bipyridine) Complex: DFT/TDDFT Study

Fedasa¹,

Negussa²,

Talema³

2020

IJCTC

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The electronic structure, absorption and emission spectra, as well as phosphorescence efficiency of Re(I) tricarbonyl complexes of a general formula fac-[Re(I)(CO) 3 (L)(R-N^N)](L = Cl; N^N = 2, 2'-bipyridine; R = -H, 1; -NO 2 , 2; -PhNO 2 , 3; -NH 2 , 4; -TPA (triphenylamine), 5) were investigated by using density functional theory(DFT) and time dependents density functional theory (TDDFT) methods. The calculated results reveal that introductions of the Electron with drawing group (EWG) and Electron donating group (EDG) on the R position of 2, 2'-bipyridine ligand. When EWG (-NO 2 and -PhNO 2 ) are introduced into complex 2 and 3, the lowest energy absorption and emission bands are red shifted compared with that of complex 1. On the contrary, the introduction of the EDG (-NH 2 and -TPA) in complex 4 and 5 cause corresponding blue shifted. The solvent effect on absorption and emission spectrum indicates that the lowest energy absorption and emission bands have red shifts with the decrease of solvent polarity. The electronic affinity (EA), ionization potential (IP) and reorganization energy (λ) results show that complex 5 is suitable to be used as an emitter in phosphorescence organic light emitting diodes (PHOLEDs). Meanwhile the emission quantum yield of complex 5 is possibly higher than that of other complexes.

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Theoretical design study on the electronic structure and photophysical properties of a series of osmium(II) complexes with different ancillary ligands

Cited by 11 publications

References 33 publications

Two Fluoro Compounds of Main Group Elements: Synthesis, Characterization, Theoretical and Spectroscopic Study

Two Fluoro Compounds of Main Group Elements: Synthesis, Characterization, Theoretical and Spectroscopic Study

Insights into the luminescent properties of anionic cyclometalated iridium(III) complexes with ligands derived from natural products

Effect of Substituents on Electronic Structure and Photophysical Properties of Re(I)(CO)<sub>3</sub>Cl(R-2, 2’-Bipyridine) Complex: DFT/TDDFT Study

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Theoretical design study on the electronic structure and photophysical properties of a series of osmium(II) complexes with different ancillary ligands

Cited by 11 publications

References 33 publications

Two Fluoro Compounds of Main Group Elements: Synthesis, Characterization, Theoretical and Spectroscopic Study

Two Fluoro Compounds of Main Group Elements: Synthesis, Characterization, Theoretical and Spectroscopic Study

Insights into the luminescent properties of anionic cyclometalated iridium(III) complexes with ligands derived from natural products

Effect of Substituents on Electronic Structure and Photophysical Properties of Re(I)(CO)&lt;sub&gt;3&lt;/sub&gt;Cl(R-2, 2’-Bipyridine) Complex: DFT/TDDFT Study

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Effect of Substituents on Electronic Structure and Photophysical Properties of Re(I)(CO)<sub>3</sub>Cl(R-2, 2’-Bipyridine) Complex: DFT/TDDFT Study