Excited state dynamics and isomerization in ruthenium sulfoxide complexes.

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.

Ultrafast spectroscopy and structural characterization of a photochromic isomerizing ruthenium bis-sulfoxide complex.

Irradiation of [Ru(bpy)2(bpSOp)](PF6)2 (where bpy is 2,2'-bipyridine and bpSOp is 1,3-bis(phenylsulfinyl)propane) results in the formation of two new isomers, namely the S,O- and O,O-bonded species. The crystal structure of the bis-thioether and bis-sulfoxide complexes are reported. NMR spectroscopy of the bis-thioether complex in solution is consistent with the molecular structure determined by diffraction methods.

Investigating the effects of solvent on the ultrafast dynamics of a photoreversible ruthenium sulfoxide complex.

The photochromic complex [Ru(bpy)2(pySO)](2+) [pySO is 2-(isopropylsulfinylmethyl)pyridine] undergoes wavelength specific, photoreversible S → O and O → S linkage isomerizations. Irradiation of the ground state S-bonded complex with blue light produces the O-bonded isomer, while irradiation of the O-bonded isomer with green light produces the S-bonded isomer. Furthermore, isomerization time constants are solvent-dependent.

Sn(IV) Schiff base complexes: triplet photosensitizers for photoredox reactions.

We present the synthesis and characterization of a series of four fluorescent Sn(iv) Schiff base complexes, which also possess long-lived triplet excited states. The complexes absorb visible light (λmax = 420 to 462 nm) and the optical properties are easily tunable without laborious synthetic elaboration. The triplet excited states are not luminescent, but can be observed and followed using nanosecond transient absorption spectroscopy.

One photon yields two isomerizations: large atomic displacements during electronic excited-state dynamics in ruthenium sulfoxide complexes.

Photochromic compounds efficiently transduce photonic energy to potential energy for excited-state bond-breaking and bond-forming reactions. A critical feature of this reaction is the nature of the electronic excited-state potential energy surface and how this surface facilitates large nuclear displacements and rearrangements. We have prepared two photochromic ruthenium sulfoxide complexes that feature two isomerization reactions following absorption of a single photon.

Sequential picosecond isomerizations in a photochromic ruthenium sulfoxide complex triggered by pump-repump-probe spectroscopy.

The complex [Ru(bpy)(2)(bpSO)](PF(6))(2), where bpy is 2,2'-bipydine and bpSO is 1,2-bis(phenylsulfinyl)ethane, exhibits three distinct isomers which are accessible upon metal-to-ligand charge-transfer (MLCT) irradiation. This complex and its parent, [Ru(bpy)(2)(bpte)](PF(6))(2), where bpte is 1,2-bis(phenylthio)ethane, have been synthesized and characterized by UV-visible spectroscopy, NMR, X-ray crystallography, and femtosecond transient absorption spectroscopy. A novel method of 2-color Pump-Repump-Probe spectroscopy has been employed to investigate all three isomers of the bis-sulfoxide complex.