Tuning the electronic and photophysical properties of platinum(II) complexes through ancillary ligand modification: a theoretical study

In this work, density functional theory and time-dependent density functional theory were used to investigate the effects of π-conjugation of the ligand on the photophysical properties, radiative/nonradiative processes and phosphorescence quantum efficiency of tetradentate cyclometalated Pt (II) complex with carbazolyl-pyridine ligands PtNON. By simulating the absorption spectra and emission wavelengths, increasing the π-conjugation of the ligand could cause the absorption and emission wavelengths to red-shift. The results of the computation of key parameters in the radiative decay process, such as singlet-triplet splitting energy, transition dipole moment and spin-coupled matrix element between the lowest triplet and singlet excited states, showed that the expansion of π-conjugation on the carbazole ligand of PtNON resulted in reduction of these parameters, thereby reducing the radiation rate constant. The analyses of the PtNON nonradiative pathway also found that the high activation energyof PtNON made it one of the reasons for the high phosphorescence quantum yield. At the same time, enhancing the molecular orbital delocalization of the ligand further enlarged the energy barrier of the nonradiative pathway, and was conducive to the improvement of phosphorescence quantum yield.

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

Zuo

Luo

Sun

et al. 2018

Applied Organom Chemis

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Upper limit to the ultimate achievable emission wavelength in near-IR emitting cyclometalated iridium complexes

Penconi

Cazzaniga

Kesarkar

et al. 2017

Photochem Photobiol Sci

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Iridium complexes bearing cyclometalated (C^N) ligands are the current emitters of choice for efficient phosphorescent organic light emitting diodes (OLEDs). Homoleptic iridium complexes Ir(C^N) and the analogous heteroleptic ones carrying a β-diketonate ancillary ligand (C^N)Ir(O^O) often exhibit similar photophysical properties and device performances; the choice among them usually depends both on the yield/ease of the respective synthetic preparations as well as on the device fabrication methods (i.e. vacuum-deposition or solution-process). In our recent study we found a significant spectral red shift on going from the homoleptic to the β-diketonate Ir(iii) derivatives. The NIR emitting complex Ir(iqbt)dpm (λ = 710 nm) has almost 20 nm red shifted emission compared to the homologue Ir(iqbt) making only the former a real NIR emitter. For comparison, we studied the Pt(iqbt)dpm complex as the suitable example to investigate metal ligand interactions. Noteworthily the Pt(iqbt)dpm emission perfectly overlaps that of the Ir(iqbt)dpm. In this paper we provide an in-depth investigation of these systems by electrochemical and spectroscopic analyses and corroborate the results with DFT and TDDFT calculations to investigate whether the Pt(ii) complex can be used as a model system to predict how far the emission can be pushed in a Ir(iii) heteroleptic derivative bearing the same C^N ligand.

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Theoretical investigation on the effect of ancillary ligand modification for highly efficient phosphorescent platinum(ii) complex design

et al. 2017

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Tuning the electronic and photophysical properties of platinum(II) complexes through ancillary ligand modification: a theoretical study

Cited by 3 publications

References 58 publications

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

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

Upper limit to the ultimate achievable emission wavelength in near-IR emitting cyclometalated iridium complexes

Theoretical investigation on the effect of ancillary ligand modification for highly efficient phosphorescent platinum(ii) complex design

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