Electron-transfer reactions and luminescent quantum yield of the triplet excited state of tetrakis[.mu.-diphosphito(2-)-p,p']diplatinate(II)

Interfacial aggregation of thioether-substituted phthalocyaninatomagnesium(ii)–palladium(ii) complexes in the toluene/water system

“…Stock solutions of 5.0 6 10 23 M metal ion were prepared by dissolving each metal chloride (99.9%) in 0.1 M hydrochloric acid. Three phthalocyanato-magnesium(II) derivatives with eight peripheral thioethers, such as (2,3,9,10,16,17,23,24-octakis-ethylthiophthalocyaninato)magnesium(II) (MgPc(SEt) 8 ), (2,3,9,10,16,17,23,24-octakis-benzylthiophthalocyaninato)magnesium(II) (MgPc(SBz) 8 ), and (2,3,9,10,16,17,23,24-octakis-benzhydrylthiophthalocyaninato)magnesium(II) (MgPc(SBh) 8 ), were synthesized. The details of synthesis were described elsewhere.…”

“…The use of coordination bonds [5][6][7][8] has some advantages in making supramolecular structures; for example, each metal center may present its own geometry and coordination number depending upon the metal element and its oxidation state. Coordinated compounds prepared from multi-dentate ligands are of great importance in recent material researches; such as electron transfer, 9 magnetic interactions, 10 optical phenomena, 11 excited-state reactivity, 12 biomimetic chemistry, 13 mixed valency, 14 and ionophoric activity. 15 Among Pc compounds, we are interested in their derivatives with sulfur atoms as coordination atoms, which have bigger van der Waals (VDW) radii than carbon, nitrogen and oxygen atoms.…”

Electronic structures and photophysics of d8-d8 complexes

“…One-electron oxidized systems are primary products of oxidative quenching of 3 dσpσ* excited states, which is a common photoreaction of bridged Rh isocyanides [15], pyrazolylbridged Ir dimers [10,11], Pt(pop) [49,56] as well as Pt(pop-BF 2 ) [89]. Upon oxidative quenching of *Rh(TMB) by methylviologen, a transient band attributable to Rh(TMB) 3+ was observed at 450 nm in MeOH (435 nm in MeCN) [15].…”

“…Triplet dσ*pσ states also are quenched by electron donors (e.g., aromatic amines) [15,49,56,89], Rh(TMB) in the presence of 1% t-butyl alcohol. Radiolysis-generated Pt(pop) 5in a phosphate buffer exhibited an intense peak at 420 nm and a weaker broad absorption at 580-600 nm that decayed with a 34 µs lifetime [133].…”

“…The 3 dσ*pσ state is quenched by energy transfer as well as by oxidative (e.g. methylviologen) and reductive (aromatic amines) electron transfer, with nearly diffusion-controlled rates (depending on driving force) and ≥80% cage-escape yields [49,56]. An interesting perfluoroborated derivative of Pt(pop) containing no hydrogen atoms, in which the pop ligands are covalently linked by BF 2 groups, was prepared recently:…”