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Ruthenium polypyridine complexes comprising sulfoxide ligands show dramatic photochromic behavior based on phototriggered S→O and O→S isomerization. Quantum yields of isomerization can be large, indicating that the excited-state bond-breaking and bond-making reactions are efficient. Ultrafast transient absorption spectroscopy reveals both adiabatic and non-adiabatic isomerization mechanisms. Incorporation of these complexes within polymer matrices leads to macroscopic bending of the polymer in an example of a direct transduction of photonic energy to mechanical energy. [ABSTRACT FROM AUTHOR]

Conspectus: Molecular photochromic compounds are those that interconvert between two isomeric forms with light. The two isomeric forms display distinct electronic and molecular structures and must not be in equilibrium with one another. These light-activated molecular switch compounds have found wide application in areas of study ranging from chemical biology to materials science, where conversion from one isomeric form to another by light prompts a response in the environment (e.g., protein or polymeric material). Certain ruthenium and osmium polypyridine sulfoxide complexes are photochromic. The mode of action is a phototriggered isomerization of the sulfoxide from S- to O-bonded. The change in ligation drastically alters both the spectroscopic and electrochemical properties of the metal complex. Our laboratory has pioneered the preparation and study of these complexes. In particular, we have applied femtosecond pump-probe spectroscopy to reveal excited state details of the isomerization mechanism. The data from numerous complexes allowed us to predict that the isomerization was nonadiabatic in nature, defined as occurring from a S-bonded triplet excited state (primarily metal-to-ligand charge transfer in character) to an O-bonded singlet ground state potential energy surface. This prediction was corroborated by high-level density functional theory calculations. An intriguing aspect of this reactivity is the coupling of nuclear motion to the electronic wave function and how this coupling affects motions productive for isomerization. In an effort to learn more about this coupling, we designed a project to examine phototriggered isomerization in bis-sulfoxide complexes. The goal of these studies was to determine whether certain complexes could be designed in which a single photon excitation event would prompt two sulfoxide isomerizations. We employed chelating sulfoxides in this study and found that both the nature of the chelate ring and the R group on the sulfoxide affect the photochemical reactivity. For example, this reactivity may be tuned such that two sulfoxide ligands isomerize sequentially following two successive excitations or that two sulfoxide ligands isomerize following a single excitation. This Account explains our understanding to date of this photochemistry. [ABSTRACT FROM AUTHOR]

Compounds of the type [Ru(tpy)(L2)(dmso))2+ (tpy is 2,2′:6′,2″-terpyridine; L2 can be 2,2′-bipyridine (bpy), N,N,N′,N′-tetramethylethylenediamine (tmen), 2-pyridine carboxylate (pic), acetylacetonate (acac), malonate (mal), or oxalate (ox)) have been studied by X-ray crystallography, electrochemistry, NMR, IR, and UV-vis spectroscopy. When L2 is bpy, tmen, or pic, the dmso ligand can be intramolecularly isomerized either electrochemically or photochemically. lsomerization is not observed when L2 is acac, mal, or ox. Isomerization results in a drastic change in the absorption spectrum, as well as in the voltammetry. Absorption maxima shift by 3470 (419-490 nm), 4775 (421-527 nm), and 4440 cm-1 (429-530 nm) for the bpy, pic, and tmen complexes, respectively. Reduction potentials for S-bonded and O-bonded complexes differ by 0.57, 0.75, and 0.62 V for the bpy, pic, and tmen complexes, respectively. Quantum yields of isomerization (ϕS→O) were determined for the bpy (0.024 ± 1), pic (0.25 ± 1), and tmen (0.007 ± 1) complexes. In comparison of these data to photosubstitution quantum yields, it appears that the isomerization mechanism does not involve the ligand field states. This result is surprising given the importance of these states in the photochemistry of ruthenium and osmium polypyridine complexes. These results and details of the mechanism are discussed. [ABSTRACT FROM AUTHOR]

Abstract: Complexes of the type [Ru(bpy)2(OSOBnR)](PF6) where bpy is 2,2′-bipyridine and OSOBnR is a 4-substituted benzylsulfinylbenzoate with R=NO2, F, Cl, H, CH3, CF3 and OCH3, have been prepared and investigated by 1H NMR spectroscopy, cyclic voltammetry and UV–vis spectroscopy. Despite the distance of the R group from ruthenium, the Ru3+/2+ reduction potential and charge transfer absorption maximum vary predictably with the electron withdrawing nature of the group. [ABSTRACT FROM AUTHOR]