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Density functional theory (DFT) calculations were performed on clusters [Os 3 (CO) 10 (α-diimine)], for α-diimine = 2,2'-bipyridine (BPY), N-isopropyl 2-iminomethylpyridine (IMP), and N, N'-diisopropyl-l,4-diaza-1,3-butadiene (DAB), together with their spectroscopic study. This important family of clusters is known to convert upon irradiation with visible light into short-lived biradicals and long-lived zwitterions from a σπ* (SBLCT) excited state that has not been described accurately thus far by quantum mechanical calculations. On the basis of the combined DFT, UV-vis absorption, and resonance Raman data, the lowest-lying visible absorption band is assigned to a σ(Os1-Os3)-to-π*(α-diimine) CT transition, for α-diimine = bpy and IMP, and to a strongly delocalized σ(Os1-Os3)π*-to-σ*(Os1-Os3)π* transition for conjugated nonaromatic α-diimine = DAB. The DFT calculations rationalize the experimentally determined characteristics of this electronic transition in the studied series: (i) The corresponding absorption band is the dominant feature in the visible spectral region. (ii) The CT character of the electronic excitation declines from α-diimine = bpy to IMP and vanishes for DAB. (iii) The excitation energies decrease in the order α-diimine = DAB &gt; BPY &gt; IMP. (iv) The oscillator strength shrinks in the order α-diimine = DAB &gt; IMP &gt; BPY. Reference photoreaction quantum yields measured accurately for the formation of a cluster zwitterion from [Os 3 (CO) 10 (IMP)] in strongly coordinating pyridine demonstrate that the optical population of the lowest-energy 1 σπ* and relaxed 3 σπ* excited states in the DFT model scheme is still capable of inducing the initial homolytic Os1-Os3 σ-bond splitting, although less efficiently than the optical excitation into neighbor higher-lying electronic transitions due to a higher potential barrier for the reaction from a dissociative (σσ*) state.

inorganic chemistry

Accurate Description of Low-Lying Excited States in a Series of Photoreactive Clusters [Os<sub>3</sub>(CO)<sub>10</sub>(α-diimine)] by DFT Calculations

Accurate Description of Low-Lying Excited States in a Series of Photoreactive Clusters [Os3(CO)10(α-diimine)] by DFT Calculations

Accurate Description of Low-Lying Excited States in a Series of Photoreactive Clusters [Os₃(CO)₁₀(α-diimine)] by DFT Calculations