Ultrafast branching in intersystem crossing dynamics revealed by coherent vibrational wavepacket motions in a bimetallic Pt(ii) complex

Abstract

Herein, we investigate the coherent vibrational wavepacket dynamics during the intersystem crossing processes in a bimetallic Pt(ii) complex.

Ligand-Structure-Dependent Coherent Vibrational Wavepacket Dynamics in Pyrazolate-Bridged Pt(II) Dimers

“…Notably, the nodal points of the two complexes appear close to the maxima of the SE features in SADS 1 (675 nm for 1 and 750 nm for 2 ). It has been previously reported in a hydroxypyridyl-bridged Pt dimer that the maximum of the SE signal and the nodal point of the CVWP motion are observed at a similar spectral position . Thus, the CVWP motions observed in the entire probe range mostly originate from the excited-state PESs.…”

“…It has been previously reported in a hydroxypyridyl-bridged Pt dimer that the maximum of the SE signal and the nodal point of the CVWP motion are observed at a similar spectral position. 50 Thus, the CVWP motions observed in the entire probe range mostly originate from the excited-state PESs.…”

Excited state processes of dinuclear Pt(ii) complexes bridged by 8-hydroxyquinoline

“…The resulting transiently formed Pt–Pt σ-bond and its vibrational motion renders these dinuclear complexes model systems for deciphering coherence phenomena in molecular excited states. 33–44…”

“…The resulting transiently formed Pt-Pt σ-bond and its vibrational motion renders these dinuclear complexes model systems for deciphering coherence phenomena in molecular excited states. [33][34][35][36][37][38][39][40][41][42][43][44] Among the various studies into Pt(II) complexes, pyrazolate bridging ligands have been extensively used in conjunction with bidentate C^N cyclometalating ligands. [45][46][47][48][49][50][51][52] Specifically, a series of pyrazolate-bridged platinum(II) complexes with the general formula [C^NPt( pz′) 2 PtC^N] (where C^N = 2-(2,4difluorophenyl)pyridyl, pz′ = μ-pyrazolate) was reported by the Thompson group in 2005.…”

Spin–vibronic mechanism at work in a luminescent square-planar cyclometalated tridentate Pt(ii) complex: absorption and ultrafast photophysics

“…[7][8][9][10][11][12] More recently, time-resolved (ps-fs) spectroscopy experiments were applied to mono-and bi-metallic Pt complexes in order to probe the interplay between nuclear and electronic motion, intersystem crossing and vibrational coherence in ultrafast processes. [13][14][15][16][17][18][19][20] This field of research opens the way to fine-tuning of the photoluminescent and charge transfer properties under stimuli such as light, electric field or a specific environment for the design of building blocks in the development of new functional and switchable materials. [21][22][23][24] Standard theoretical investigations, based on routine static density functional theory (DFT) and time-dependent DFT (TD-DFT) calculations, are not up to the experimental challenges.…”