Theoretical insight into the photodeactivation pathway of the tetradentate Pt(II) complex: The π‐conjugation effect

Zuo, Ke; Luo, Yafei; Sun, Xin; Shen, Wei; Tang, Dianyong; Hu, Jianping

doi:10.1002/aoc.4220

Cited by 7 publications

(4 citation statements)

References 53 publications

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“…Based on the crystal structures resolved here, the geometries of all packing patterns in the ground (S 0 ) and excited states (T 1 ) were optimized using the restricted and unrestricted density functional theory methods with the PBE0 functional. − The frequency of the optimized geometries was calculated to check that all of the stationary points were either minima. In order to simulate the influence of polarization effects of the crystal environment, the polarizable continuum model (PCM) was also taken into account. , On the basis of the optimized structures, the time-dependent DFT (TD-DFT) method was employed to investigate the vertical emission energies.…”

Section: Methodsmentioning

confidence: 99%

Temperature-Independent Ultralong Organic Phosphorescence with a Symmetrical Butterfly-Type Structure

Xiao

Lou

Zuo

et al. 2022

Crystal Growth & Design

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Room-temperature phosphorescence (RTP) materials in the solid state have been attracting widespread attention and found broad prospects in the fields of smart wear, optoelectronic devices, bioimaging, and encryption. However, purely organic RTP materials are still scarce due to weak spin−orbit coupling and fast nonradiative transition under ambient conditions. Here, we developed a facile strategy using the heavy-atom effect to construct RTP materials of commercial/lab-synthesized carbazole-based derivatives (DCzB-X/DCzB-X-lab). DCzB-Cl, DCzB-Br, and DCzB-I synthesized with commercial carbazole have ultralong phosphorescence lifetimes of 789.0, 184.3, and 49.6 ms, respectively, much longer than those of lab-synthesized carbazole derivative due to the presence of isomers in the commercial samples. Combined with the single-crystal structure and theoretical calculation analysis, the compact packing mode of the butterfly-type packing style (BPS) with a halogen substituent is favorable for persistent phosphorescence. Impressively, an unusual phenomenon was found, which shows that the phosphorescence lifetime of DCzBhalogen does not increase with the decrease of temperature, indicating that BPS can effectively suppress the nonradiative transition. The results break through the traditional low-temperature-enhanced phosphorescence theory and provide a new platform to rationally design highly efficient RTP materials.

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Section: Methodsmentioning

confidence: 99%

Temperature-Independent Ultralong Organic Phosphorescence with a Symmetrical Butterfly-Type Structure

Xiao

Lou

Zuo

et al. 2022

Crystal Growth & Design

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“…The ZFS of organometallic complexes is dependent not only on the type of the central element of the complexes but also on the chelating scheme, thereby, some Pt(II) complexes can possess slightly higher values of ZFS . The theoretical estimation of the ZFS value for the representative tetradentate Pt(II) complex is about 70 cm –1 (ref ). In this regard, we assume applicability of the isotropic averaging scheme for the description of the triplet manifold relaxation in the target tetradentate Pt(II) complexes and use eqs and in all subsequent calculations.…”

Section: Theorymentioning

confidence: 99%

Tetradentate Pt(II) Phosphors: A Computational Analysis of Nonradiative Decay Rates and Luminescence Efficiency

et al. 2020

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Cyclometalated tetradentate Pt(II) complexes are a promising class of phosphors used in organic light-emitting diodes (OLEDs). We calculated decay rates and the resulting photoluminescence quantum yield (PLQY) for 17 recently reported tetradentate Pt(II) complexes designed for OLED application. Several theoretical approaches for treating the vibrational density of states in decay processes were utilized and systematically compared using ab initio calculations as a source of input data. It was shown that along with the direct spin–orbit coupling and energy gap between initial and final states of transition, a proper account for nuclear reorganization is required for the correct description of the relaxation process. Among different approaches for calculation of the nonradiative decay rate, the approximation constructed with the separate treatment of the slow and fast normal modes was found to be the most accurate. The estimated error in prediction of the PLQY is about 10%, which allows to consider the formulated method as suitable for practical application in the development of new Pt(II) OLED phosphors.

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“…Che et al [10][11][12] reported a series of Pt(II) complex with rigid four-tooth [O^N^C^N] ligands, and they all showed good quantum yield, the highest of which could reach 0.90. The calculation results of Luo et al [13,14] show that π-conjugation can effectively reduce the non-radiation rate constant of the complex. By expanding the π-conjugated system, it is found that the emission wavelength becomes longer and the radiation rate constant decreases.…”

Section: Introductionmentioning

confidence: 98%

A promising strategy for increasing phosphorescent quantum yield: The ligand 10‐cyclic chelate of the tetradentate Pt(II) complex

Gao

Shi

Luo

et al. 2021

Applied Organom Chemis

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In this paper, the density functional theory (DFT) and time-dependent density functional theory (TD-DFT) were used to deeply investigate the photophysical properties and radiative and non-radiative processes of tetradentate Pt(II) complexes with 10-and 11-cyclic chelate ligands. According to the calculated results, the cyclization of ligand can distinctly influence on the emission wavelengths of complexes. In addition, due to the larger spin density, spin-orbit coupling (SOC) matrix element, and smaller metal-centered d-d excited states ( 3 MC) character, singlet-triplet splitting energy (ΔE(S n À T 1 )), the radiation rate constant (k r = 5.9E + 04) of the 10-cyclic chelate ligand complex is significantly higher than that of the 11-cyclic chelate ligand complex (k r = 1.9E + 04). In the case of temperature-dependent non-radiative process, compared with 11-cyclic chelate ligand complex, 10-cyclic chelate ligand complex should possess the larger non-radiative rate because of the lower energy barrier from the excited state to 3 MC. What's more, the 10-cyclic chelate ligand complex has small Huang-Rhys factor, which suggests that the 10-cyclic chelate ligand complex has better rigidity and color purity. This investigation could provide some useful information for designing the highperformance organic light-emitting diode (OLED) materials. K E Y W O R D S 10-and 11-cyclic chelate ligands, density functional theory, organic light-emitting diodes (OLEDs), tetradentate Pt(II) complex Jianping Hu and Dianyong Tang contributed equally to this work.

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Theoretical insight into the photodeactivation pathway of the tetradentate Pt(II) complex: The π‐conjugation effect

Cited by 7 publications

References 53 publications

Temperature-Independent Ultralong Organic Phosphorescence with a Symmetrical Butterfly-Type Structure

Temperature-Independent Ultralong Organic Phosphorescence with a Symmetrical Butterfly-Type Structure

Tetradentate Pt(II) Phosphors: A Computational Analysis of Nonradiative Decay Rates and Luminescence Efficiency

A promising strategy for increasing phosphorescent quantum yield: The ligand 10‐cyclic chelate of the tetradentate Pt(II) complex

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