Photoisomerization in an analogous set of ruthenium sulfoxide complexes

Porter, Brianne L.; McClure, Beth Anne; Abrams, Eric R.; Engle, James T.; Ziegler, Christopher J.; Rack, Jeffrey J.

doi:10.1016/j.jphotochem.2010.11.002

Cited by 9 publications

(7 citation statements)

References 46 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[28,29] In this scenario, isomerization (chemical) is triggered following oxidation (electrochemical) from Os II to Os III or following reduction of Os III to Os II . For certain ruthenium and osmium sulfoxide complexes, evidence for SǞO isomerization appears through irreversible couples that are typically analyzed by an ECEC (Electrochemical-Chemical Electrochemical-Chemical) square scheme mechanism.…”

Section: Resultsmentioning

confidence: 99%

“…Cyclic voltammograms of [Os(bpy) 2 (pySO)] 2+ and [Os(bpy) 2 (pySOCF 3 )] 2+ feature reversible one‐electron couples that are ascribed to Os 3+/2+ reduction potentials ( E °′) at 1.01 V (vs Ag/AgCl; $\tilde {\nu}$ = 0.1 V/s; CH 3 CN; 0.1 M TBAPF 6 ) and 1.17 V, respectively (see Supporting Information, Figures S1 and S2). For certain ruthenium and osmium sulfoxide complexes, evidence for S→O isomerization appears through irreversible couples that are typically analyzed by an ECEC (Electrochemical‐Chemical Electrochemical‐Chemical) square scheme mechanism 28,29. In this scenario, isomerization (chemical) is triggered following oxidation (electrochemical) from Os II to Os III or following reduction of Os III to Os II .…”

Section: Resultsmentioning

confidence: 99%

See 1 more Smart Citation

A Flexible Chelate Leads to Phototriggered Isomerization in an Osmium Sulfoxide Complex

2012

Self Cite

View full text Add to dashboard Cite

We report the preparation and spectroscopic properties of [Os(bpy) 2 (pySO)] 2+ and [Os(bpy) 2 (pySOCF 3 )] 2+ , where bpy is 2,2Ј-bipyridine, pySO is 2-(propane-2-sulfinylmethyl)pyridine, and pySOCF 3 is 2-[(trifluoroethylsulfinyl)methyl]pyridine. The charge-transfer absorption spectra of [Os(bpy) 2 -(pySO)] 2+ and [Os(bpy) 2 (pySOCF 3 )] 2+ are 378 and 367 nm, respectively. Charge-transfer excitation of [Os(bpy) 2 -(pySOCF 3 )] 2+ shows substantial changes in the UV/Vis spectrum with a shift in the lowest energy absorption maximum from 367 to 415 nm, which is consistent with phototriggered SǞO isomerization. Irradiation of [Os(bpy) 2 (pySO)] 2+ shows no evidence of isomerization. Cyclic voltammograms of [Os(bpy) 2 (pySO)] 2+ and [Os(bpy) 2 (pySOCF 3 )] 2+ feature reversible one-electron couples that are ascribed to Os 3+/2+ reduction potentials (E°Ј) at 1.01 V (vs Ag/AgCl; ν = 0.1 V/s; CH 3 CN; 0.1 M TBAPF 6 ) and 1.17 V, respectively. Femto-

show abstract

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

A Flexible Chelate Leads to Phototriggered Isomerization in an Osmium Sulfoxide Complex

2012

Self Cite

View full text Add to dashboard Cite

show abstract

“…Since isomerization is prompted by oxidation in this model, transition metal complexes that do not feature metal oxidation will not prompt isomerization. We wanted to revisit this concept of structural changes to elicit control of photoisomerization in chelating sulfoxides, but our study of benzoate and pyridine sulfoxides revealed only modest control . We felt a new chelating sulfoxide architecture based on phosphines would be successful, as phosphines are widely employed in organometallic chemistry to modulate electron density at the metal .…”

Section: Photochromic Ruthenium Phosphine Sulfoxide Complexesmentioning

confidence: 99%

“…We wanted to revisit this concept of structural changes to elicit control of photoisomerization in chelating sulfoxides, but our study of benzoate and pyridine sulfoxides revealed only modest control. 27 We felt a new chelating sulfoxide architecture based on phosphines would be successful, as phosphines are widely employed in organometallic chemistry to modulate electron density at the metal. 28 This is achieved by variation of the R groups on the phosphine, permitting phosphines to be σonly donors (e.g., PR 3 , R is alkyl), σand π-donors (e.g., phosphites), or σand π-acceptors (e.g., PPh 3 , Ph is phenyl).…”

Section: Sulfoxide Complexesmentioning

confidence: 99%

A Future Perspective on Phototriggered Isomerizations of Transition Metal Sulfoxides and Related Complexes

et al. 2021

Self Cite

View full text Add to dashboard Cite

Photochromic molecules are examples of light-activated bistable molecules. We highlight the design criteria for a class of ruthenium and osmium sulfoxide complexes that undergo phototriggered isomerization of the bound sulfoxide. The mode of action in these complexes is an excited-state isomerization of the sulfoxide from S-bonded to O-bonded. We discuss the basic mechanism for this transformation and highlight specific examples that demonstrate the effectiveness and efficiency of the isomerization. We subsequently discuss future research directions within the field of phototriggered sulfoxide isomerizations on transition metal polypyridine complexes. These efforts involve new synthetic directions, including the choice of metal as well as new ambidentate ligands for isomerization.

show abstract

“…Also, the bistability of these organometallic photochromes requires an adequate free energy of activation (Δ G ⧧ > ∼30 kcal mol –1 ) for rearrangement such that the complex will not thermally isomerize between chelates at room temperature. Hence, the ground-state bond dissociation enthalpy (BDE) required to cleave a metal–ligand bond is of particular interest to researchers to aid in the rational design of new organometallic photochromes. ,,− Our lab and others have used photoacoustic calorimetry (PAC) to study the BDEs of various ligands in transition-metal (TM) complexes. − ,,,− …”

Section: Introductionmentioning

confidence: 99%

Calibrating Reaction Enthalpies: Use of Density Functional Theory and the Correlation Consistent Composite Approach in the Design of Photochromic Materials

et al. 2016

View full text Add to dashboard Cite

Acquisition of highly accurate energetic data for chromium-containing molecules and various chromium carbonyl complexes is a major step toward calibrating bond energies and thermal isomerization energies from mechanisms for Cr-centered photochromic materials being developed in our laboratories. The performance of six density functionals in conjunction with seven basis sets, utilizing Gaussian-type orbitals, has been evaluated for the calculation of gas-phase enthalpies of formation and enthalpies of reaction at 298.15 K on various chromium-containing systems. Nineteen molecules were examined: Cr(CO), Cr(CO), Cr(CO)(CH), Cr(CO)(CClH), Cr(CO)(cis-(CClH)), Cr(CO)(gem-(CClH)), Cr(CO)(trans-(CClH)), Cr(CO)(CClH), Cr(CO)(CCl), CrO, CrF, CrCl, CrCl, CrBr, CrBr, CrOCl, CrOCl, CrOF, and CrOF. The performance of 69 density functionals in conjunction with a single basis set utilizing Slater-type orbitals (STO) and a zeroth-order relativistic approximation was also evaluated for the same test set. Values derived from density functional theory were compared to experimental values where available, or values derived from the correlation consistent composite approach (ccCA). When all reactions were considered, the functionals that exhibited the smallest mean absolute deviations (MADs, in kcal mol) from ccCA-derived values were B97-1 (6.9), VS98 (9.0), and KCIS (9.4) in conjunction with quadruple-ζ STO basis sets and B97-1 (9.3) in conjunction with cc-pVTZ basis sets. When considering only the set of gas-phase reaction enthalpies (ΔH°), the functional that exhibited the smallest MADs from ccCA-derived values were B97-1 in conjunction with cc-pVTZ basis sets (9.1) and PBEPBE in conjunction with polarized valence triple-ζ basis set/effective core potential combination for Cr and augmented and multiple polarized triple-ζ Pople style basis sets (9.5). Also of interest, certainly because of known cancellation of errors, PBEPBE with the least-computationally expensive basis set combination considered in the present study (valence double-ζ basis set/effective core potential combination for Cr and singly-polarized double-ζ Pople style basis sets) also provided reasonable accuracy (11.1). An increase in basis set size was found to have an improvement in accuracy for the best performing functional (B97-1).

show abstract

Photoisomerization in an analogous set of ruthenium sulfoxide complexes

Cited by 9 publications

References 46 publications

A Flexible Chelate Leads to Phototriggered Isomerization in an Osmium Sulfoxide Complex

A Flexible Chelate Leads to Phototriggered Isomerization in an Osmium Sulfoxide Complex

A Future Perspective on Phototriggered Isomerizations of Transition Metal Sulfoxides and Related Complexes

Calibrating Reaction Enthalpies: Use of Density Functional Theory and the Correlation Consistent Composite Approach in the Design of Photochromic Materials

Contact Info

Product

Resources

About