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

Daniel, Chantal; Mandal, Souvik

doi:10.1039/d3cp01890c

Cited by 5 publications

(3 citation statements)

References 63 publications

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“…Our aim is not to determine accurate vibronic spectra for a direct comparison with highly resolved experimental absorption and/or ECD spectra, 16,26,27 but to select the most promising molecules on the basis of the electronic and structural properties of their excited states prior to an experimental validation. All the calculations are based on Kohn–Sham density functional theory (KS-DFT) including solvent and SOC corrections.…”

Section: Resultsmentioning

confidence: 99%

Chiroptical activity of benzannulated N-heterocyclic carbene rhenium(i) tricarbonyl halide complexes: towards efficient circularly polarized luminescence emitters

Giuso,

Gourlaouen,

Delporte--Pébay

et al. 2024

Phys. Chem. Chem. Phys.

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Section: Resultsmentioning

confidence: 99%

Chiroptical activity of benzannulated N-heterocyclic carbene rhenium(i) tricarbonyl halide complexes: towards efficient circularly polarized luminescence emitters

Giuso,

Gourlaouen,

Delporte--Pébay

et al. 2024

Phys. Chem. Chem. Phys.

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“…Moreover, spin-orbit and vibronic effects could aslo modify the fine structure of the calculated spectra. [33] A comparison between scalar and spin-orbit absorption spectra of complex 1 (Figure S4, Supporting Information) indicates that SOC effects are negligible here. Nevertheless, a qualitative assignment of the experimental bands is justified to decipher the broad experimental absorption.…”

Section: Computational Investigationmentioning

confidence: 93%

Binuclear Biphenyl Organogold(III) Complexes: Synthesis, Photophysical and Theoretical Investigation, and Anticancer Activity

Giuso,

Yang,

Forté

et al. 2023

ChemPlusChem

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A series of four binuclear complexes of general formula [(C^C)Au(Cl)(L^L)(Cl)Au(C^C)], where C^C is 4,4’‐diterbutylbiphenyl and L^L is either a bridging diphosphine or 4,4’‐bipyridine, are synthetized with 52 to 72 % yield and structurally characterized by X‐ray diffraction. The use of the chelating 1,2‐diphenylphosphinoethane ligand in a 1:2 (P^P):Au stoichiometry leads to the near quantitative formation of a gold double‐complex salt of general formula [(C^C)Au(P^P)][(C^C^)AuCl2]. The compounds display long‐lived yellow‐green phosphorescence with λem in the range of 525 to 585 nm in the solid state with photoluminescence quantum yields (PLQY) up to 10%. These AuIII complexes are tested for their antiproliferative activity against lung adenocarcinoma cells A549 and results show that compounds 2 and 5 are the most promising candidates. The digold salt 5 shows anticancer activity between 66 and 200 nM on the tested cancer cell lines, whereas derivative 2 displays concentration values required to reduce by 50% the cell viability (IC50) between 7 and 11 mM. Reactivity studies of compound 5 reveal that the [(C^C)Au(P^P)]+ cation is stable in the presence of relevant biomolecules including glutathione suggesting a structural mechanism of action.

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“…Moreover, important data on SOC as well as vibrational mode activities in the nuclear relaxed structure, in both the ground state and excited states, can be obtained. However, quantum simulations beyond the Born–Oppenheimer (BO) approximation considering the interplay and coupling between the active electronic excited states and the nuclear vibrational state manifold are required to model the nonadiabatic dynamics in real time and to decipher the spin-vibronic mechanism underlying the ultrafast competitive excited state decays. − …”

Section: Introductionmentioning

confidence: 99%

Ultrafast Excited-State Nonadiabatic Dynamics in Pt(II) Donor–Bridge–Acceptor Assemblies: A Quantum Approach for Optical Control

Mandal,

Daniel

2024

J. Phys. Chem. A

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The ultrafast nonadiabatic excited state dynamics of (PTZ-N-benzyl-acetylide) (trans-bis-trimethylphosphine) Pt(II) (acetylide-NDI-bis-methyl) 1, representative of a series of Pt(II) donor−bridge−acceptor assemblies experimentally studied by the Weinstein group, University of Sheffield, is investigated by means of wavepacket propagations based on the multiconfiguration timedependent Hartree (MCTDH) method. On the basis of electronic structure data obtained at the time-dependent density functional theory (TD-DFT) level, the subpicosecond decay is simulated by solving an 11 electronic states multimode problem, up to 18 vibrational normal modes, including both spin−orbit coupling (SOC) and vibronic coupling. A careful analysis of the results, within the diabatic representation, provides the key features of the spin−vibronic mechanism at work in this complex, distinguishing between the spin−orbit and vibronically activated ultrafast processes within the excited states manifold. The knowledge of the key active normal modes that promote selectively the population of specific electronic excited states opens a route toward optical control by selectively exciting these modes in order to drive the associated nonadiabatic processes. Relevant simulations, over 2 ps, are proposed to assess the impact of these selective vibrational excitations on the branching ratio between the primary photoproducts, namely, bridge−acceptor charge-transfer (CT) and donor−acceptor charge-separated (CS) electronic states. Whereas the excitation of the localized acetylide bridge C�C bond stretching does not modify drastically the population of the low-lying electronic states within the first two ps, vibrational excitation of the out-of-plane twisting motion of the N-benzyl group linked to the donor entity favors the population of the 1,3 CS states at the expense of the lowest 1,3 CT states. This quantum study opens the route to IR optical control experiments based on the specific alteration of vibrational normal modes that activate vibronic couplings between key electronic excited states. However, the presence of critical crossings along the PES channels associated with these normal modes and the role of concurrent SOC driven ultrafast transfers of population should not be underestimated.

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

Abstract: The absorption spectrum of [Pt(dpybMe)Cl] (dpyb = 2,6-di-(2-pyridyl)benzene), representative of luminescent halide-substituted tridentate cyclometalated square planar Pt(II) neutral complexes, have been revisited by means of non-adiabatic wavepacket quantum dynamics. The...

Cited by 5 publications

References 63 publications

Chiroptical activity of benzannulated N-heterocyclic carbene rhenium(i) tricarbonyl halide complexes: towards efficient circularly polarized luminescence emitters

Chiroptical activity of benzannulated N-heterocyclic carbene rhenium(i) tricarbonyl halide complexes: towards efficient circularly polarized luminescence emitters

Binuclear Biphenyl Organogold(III) Complexes: Synthesis, Photophysical and Theoretical Investigation, and Anticancer Activity

Ultrafast Excited-State Nonadiabatic Dynamics in Pt(II) Donor–Bridge–Acceptor Assemblies: A Quantum Approach for Optical Control

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