A theoretical research on intersystem crossing, radiative and nonradiative rates of cyclometalated platinum(II) complexes

Yang, Biwei; Huang, Shuang; Luo, Shiping

doi:10.1007/s00214-019-2466-6

Cited by 6 publications

(3 citation statements)

References 52 publications

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“…It can also be of importance in a great variety of other applications such as in organic photocatalysis and solar energy harvesting [10][11][12]. Photosensitizers often contain transition metals [13] such as Ru, [14] Pd [15] and Pt [16,17]. In these complexes, intersystem crossing (ISC) is efficient due to spin-orbit interactions, [18] a relativistic effect usually present in atoms with large nuclei, commonly called the heavy-atom effect.…”

Section: Introductionmentioning

confidence: 99%

Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene—Dimethylaniline

et al. 2022

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The conformational dependence of the matrix element for spin–orbit coupling and of the electronic coupling for charge separation are determined for an electron donor–acceptor system containing a pyrene acceptor and a dimethylaniline donor. Different kinetic and energetic aspects that play a role in the spin–orbit charge transfer intersystem crossing (SOCT-ISC) mechanism are discussed. This includes parameters related to initial charge separation and the charge recombination pathways using the Classical Marcus Theory of electron transfer. The spin–orbit coupling, which plays a significant role in charge recombination to the triplet state, can be probed by (TD)-DFT, using the latter as a tool to understand and predict the SOCT-ISC mechanism. The matrix elements for spin–orbit coupling for acetone and 4-thio-thymine are used for benchmarking. (Time Dependent-) Density Functional Theory (DFT and TD-DFT) calculations are applied using the quantum chemical program Amsterdam Density Functional (ADF).

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Section: Introductionmentioning

confidence: 99%

Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene—Dimethylaniline

et al. 2022

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“…In recent decades, luminescent platinum(II) complexes have attracted considerable attention and shown diverse applications in various fields, such as organic light-emitting devices, − photocatalysts, , and sensors. − The heavy metal atom (Pt) has the strong spin–orbit coupling (SOC) and induces efficient singlet to triplet intersystem crossing (ISC), and thus, the platinum(II) complexes can harvest both singlet and triplet electrogenerated excitons in devices, achieving 100% internal quantum efficiency theoretically. − Consequently, platinum(II) complexes can be used as excellent phosphorescent emitters in the preparation of organic light-emitting diodes (OLEDs) . Among these emitters studied, cycloplatinated(II) complexes based on bidentate, tridentate, or tetradentate ligands have been extensively presented and investigated as valuable luminescent materials. − However, square-planar geometries of platinum(II) complexes are prone to cause to aggregate through intermolecular Pt–Pt and π–π interactions, arising triplet–triplet annihilation and concentration quenching, thereby seriously undermining emission efficiencies. , Given that the emission efficiencies of cycloplatinated(II) complexes can be effectively improved by increasing the structural rigidity of scaffolds, − one of the effective strategies to gain complexes with superior emission efficiencies is to introduce bulky substituents (such as the bulky triphenylphosphine oxide group (OPPh 3 ) and triphenylphosphine (PPh 3 ) groups) to rigidify the ancillary ligands.…”

Section: Introductionmentioning

confidence: 99%

Highly Emissive Platinum(II) Complexes Bearing Bulky Phenyltriazolate Ligands: Synthesis, Structure, and Photophysics

et al. 2022

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Dinuclear and mononuclear cycloplatinated(II) complexes (1−3 and 4−6) with formulas [Pt(bt)(μ-L)] 2 and Pt(bt)(L) [bt = 2-phenylbenzothiazole, μ-L = deprotonated diphenyl(2-(5-phenyl-4H-1,2,4-triazol-3yl)phenyl)phosphine oxide derivatives for L1−L3, and L = deprotonated 3-(2-(diphenylphosphino)phenyl)-5-phenyl-4H-1,2,4-triazole derivatives for L4−L6]have been successfully synthesized and systematically characterized. Singlecrystal X-ray analysis demonstrates that these complexes exhibit distorted square-planar geometries around Pt(II) centers. There are no apparent intermolecular π−π and Pt−Pt interactions owing to the presence of bulky ligands. Therefore, these complexes achieve excellent monomeric emission in solution, PMMA films, and the solid state with a photoluminescence quantum yield (Φ) up to 67.3% in the solid state. The photophysical behaviors associated with theoretical investigations reveal that the emissions of these complexes possess primarily a 3 LC feature together with some 3 MLCT character.

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“…10,11,12 Photosensitizers often contain transition metals 13 such as Ru, 14 Pd 15 and Pt. 16,17 In these complexes, intersystem crossing (ISC) is efficient due to spin-orbit interactions, 18 a relativistic effect usually present in atoms with large nuclei, commonly called the heavy-atom effect. The corresponding ISC is known as spin-orbit intersystem crossing (SO-ISC).…”

Section: Introductionmentioning

confidence: 99%

Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene - Dimethylaniline

Bissesar¹,

Raamsdonk²,

Gibbons³

et al. 2021

Preprint

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The conformational dependence of the matrix element for spin-orbit coupling and of the electronic coupling for charge separation are determined for an electron donor-acceptor system containing a pyrene acceptor and a dimethylaniline donor. Different kinetic and energetic aspects that play a role in the spin-orbit charge transfer intersystem crossing (SOCT-ISC) mechanism are discussed. This includes parameters related to initial charge separation and the charge recombination pathways using the (Semi-Classical) Marcus Theory for electron transfer. The spin-orbit coupling, which plays a significant role in charge recombination to the triplet state can be probed by (TD-)DFT, using the latter as a tool to understand and predict the SOCT-ISC mechanism. The matrix elements for spin-orbit coupling for acetone and 4-thio-thymine are used for benchmarking. (Time Dependent-) Density Functional Theory (DFT and TD-DFT) calculations are applied using the quantum chemical program Amsterdam Density Functional (ADF).

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A theoretical research on intersystem crossing, radiative and nonradiative rates of cyclometalated platinum(II) complexes

Cited by 6 publications

References 52 publications

Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene—Dimethylaniline

Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene—Dimethylaniline

Highly Emissive Platinum(II) Complexes Bearing Bulky Phenyltriazolate Ligands: Synthesis, Structure, and Photophysics

Spin Orbit Coupling in Orthogonal Charge Transfer States: (TD-)DFT of Pyrene - Dimethylaniline

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