▪ Abstract Proton-coupled electron transfer (PCET) is an important mechanism for charge transfer in a wide variety of systems including biology- and materials-oriented venues. We review several are...

/pdf/proton-coupled-electron-transfer-3oyvp0w9qd.pdf

Proton-Coupled Electron Transfer

A method of detecting the presence or absence of saccharide or saccharide level in a biological or artificial sample comprising contacting the sample with a water-soluble tetraphenylethene-cored probe having multiple functionalities of boronic acid and aggregation induced emission (AIE) characteristics, and detecting fluorescence. A method for detecting pH in a sample solution with a certain pH value comprising contacting the sample solution with a water-soluble tetraphenylethene-cored probe having multiple functionalities of boronic acid and aggregation induced emission (AIE) characteristics, and detecting fluorescence.

Specific detection of D-glucose by a tetraphenylethene-base fluorescent sensor

Carbohydrates as ligands: coordination equilibria and structure of the metal complexes

Bifunctional chelators for therapeutic lanthanide radiopharmaceuticals.

The molecular structure and dynamics of the photoexcited metal-to-ligand-charge-transfer (MLCT) state of [CuI(dmp)2]+, where dmp is 2,9-dimethyl-1,10-phenanthroline, in acetonitrile have been investigated by time-domain pump-probe X-ray absorption spectroscopy, femtosecond optical transient spectroscopy, and density functional theory (DFT). The time resolution for the excited state structural determination was 100 ps, provided by single X-ray pulses from a third generation synchrotron source. The copper ion in the thermally equilibrated MLCT state has the same oxidation state as the corresponding copper(II) complex in the ground state and was found to be penta-coordinate with an average nearest neighbor Cu−N distance 0.04 A shorter than that of the ground state [CuI(dmp)2]+. The results confirm the previously proposed “exciplex” structure of the MLCT state in Lewis basic solvents. The evolution from the photoexcited Franck-Condon MLCT state to the thermally equilibrated MLCT state was followed by femtosec...

/pdf/mlct-state-structure-and-dynamics-of-a-copper-i-diimine-4c740buxwx.pdf

MLCT state structure and dynamics of a copper(I) diimine complex characterized by pump-probe X-ray and laser spectroscopies and DFT calculations.

Complexes of tridentate and pentadentate macrocyclic ligands

A method of marking an industrial process material including selectively incorporating a luminescent marker onto and/or into the industrial process material in a trace amount insufficient to be optically detectable in the presence of ambient light but sufficient to be non-destructively optically detectable in and/or on the industrial proce material in situ in the field or on-site. The trace amount of the luminescent marker is used to track, identify authenticate the industrial process material for at least one of material control, inventory control, stock control, logistics control, quality control and pollution control.

High-resolution tracking of industrial process materials using trace incorporation of luminescent markers

The mechanisms of oxidative ligand dehydrogenation in high-valent ruthenium hexaamine complexes of bidentate 1,2-ethanediamine (en) and tridentate 1,1,1-tris(aminomethyl)ethane (tame) are elucidated in detail. In basic aqueous solution, [RuIII(tame)2]3+ undergoes rapid initial deprotonation (pKIII = 10.3). This is followed by a pH-dependent disproportionation step involving either [RuIII(tame)2-H+]2+ + [RuIII(tame)2]3+ (k1d = 8300 M-1 s-1) or two singly deprotonated [RuIII(tame)2-H+]2+ ions (k2d = 3900 M-1 s-1). The products are [RuII(tame)2]2+ and either the singly deprotonated species [RuIV(tame)2-H+]3+ (pKIV = 8.2) or the doubly deprotonated [RuIV(tame)2-2H+]2+. These Ru(IV) complexes undergo spontaneous dehydrogenation to give the imine [RuII(imtame)(tame)]2+ (imtame = 1,1-bis(aminomethyl)-1-(iminomethyl)ethane), with first-order rate constants of k1im = 320 s-1 and k2im = 1.1 s-1, respectively. In the [RuIII(en)3]3+ system, the initial deprotonation (pKIII = 10.4) is followed by the corresponding dis...

Ligand Dehydrogenation in Ruthenium-Amine Complexes: Reactivity of 1,2-Ethanediamine and 1,1,1-Tris(aminomethyl)ethane.

The oxidation of cobalt(II) by [Co(ox) 3 ] 3- in 1,2-diaminoethane solutions proceeds by both inner-sphere and outer-sphere pathways leading to formation of [Co(en) 2 (ox)] + and [Co(en) 3 ] 3+ with rate constants 3300 and 390 M -1 s -1 , respectively, at 25.0˚C and 0.10 M ionic strength

Stereoselectivity in the reduction of [Co(ox)3]3− by [Co(en)3]2+ and its derivatives

Electron transfer kinetics for the reduction of spinach plastocyanin and horse cytochrome c by several cobalt-cage complexes have been determined. The reduction of plastocyanin by [Co((N(CH 3 ) 3 ) 2 -sar)] 4+ shows saturation kinetics with K Co(II) = (1.5±0.2)×10 3 M -1 , and κ' et =4.0±0.2 s -1 . This reaction is stereoselective (κ Δ /κ Δ = 1.7) and the stereoselectivity is independent of ionic strength.

Peter Osvath

Papers

Complexes of tridentate and pentadentate macrocyclic ligands

High-resolution tracking of industrial process materials using trace incorporation of luminescent markers

Ligand Dehydrogenation in Ruthenium-Amine Complexes: Reactivity of 1,2-Ethanediamine and 1,1,1-Tris(aminomethyl)ethane.

Stereoselectivity in the reduction of [Co(ox)3]3− by [Co(en)3]2+ and its derivatives

Metalloprotein-cobalt cage electron transfer and the stereoselective reduction of spinach plastocyanin by .LAMBDA.- and .DELTA.-[Co((N(CH3)3)2-sar)]4+