Revealing Hot and Long-Lived Metastable Spin States in the Photoinduced Switching of Solvated Metallogrid Complexes with Femtosecond Optical and X-ray Spectroscopies.
Maria A NaumovaAleksandr KalinkoJoanne W L WongMohamed AbdellahHuifang GengEdoardo DomenichiniJie MengSol Alvarez GutierrezPierre-Adrien ManteWeihua LinPeter ZaldenAndreas GallerFrederico LimaKatharina KubicekMykola BiednovAlexander BritzStefano ChecchiaVictoria KabanovaMichael WulffJennifer ZimaraDirk SchwarzerSerhiy DemeshkoVadim Yu MurzinDavid J GosztolaMartin JarenmarkJianxin ZhangMatthias BauerLatévi Max Lawson DakuWojciech GaweldaDmitry KhakhulinChristian BresslerFranc MeyerKaibo ZhengSophie E CantonPublished in: The journal of physical chemistry letters (2020)
An atomistic understanding of the photoinduced spin-state switching (PSS) within polynuclear systems of d4-d7 transition metal ion complexes is required for their rational integration into light-driven reactions of chemical and biological interest. However, in contrast to mononuclear systems, the multidimensional dynamics of the PSS in solvated molecular arrays have not yet been elucidated due to the expected complications associated with the connectivity between the metal centers and the strong interactions with the surroundings. In this work, the PSS in a solvated triiron(II) metallogrid complex is characterized using transient optical absorption and X-ray emission spectroscopies on the femtosecond time scale. The complementary measurements reveal the photoinduced creation of energy-rich (hot) and long-lived quintet states, whose dynamics differ critically from their mononuclear congeners. This finding opens major prospects for developing novel schemes in solution-phase spin chemistry that are driven by the dynamic PSS process in compact oligometallic arrays.
Keyphrases
- transition metal
- high resolution
- electron transfer
- room temperature
- single molecule
- density functional theory
- peripheral blood
- high speed
- dual energy
- magnetic resonance
- high density
- functional connectivity
- molecular dynamics simulations
- resting state
- genome wide
- risk factors
- magnetic resonance imaging
- gene expression
- current status
- computed tomography
- blood brain barrier
- electron microscopy
- contrast enhanced
- solid state