ChemInform Abstract: Temperature Dependence of the Photoinduced Disproportionation of Ru(bpy)2+ 3 on Porous Vycor Glass.

Fan, Jianwei; Shi, Wei; Tysoe, Steven A.; Strekas, Thomas C.; Gafney, Harry D.

doi:10.1002/chin.198917303

Cited by 2 publications

(3 citation statements)

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“…This may be an electrostatic effect mediated by increased negative charge density at the substrate surface via the BPDC SAM layer. Electrostatic interactions of this type are not uncommon between RuBPY and metal oxides such as SnO 2 , TiO 2 , and SiO 2 . ,,, Interestingly, the effect appears to be more pronounced on glass relative to FTO when taking into account the inability to produce less than 10 m m doped films on glass. This would imply a higher anionic surface charge density lending to increased localized RuDCBPY concentrations at the glass substrate surface relative to FTO.…”

Section: Resultsmentioning

confidence: 99%

“…Electrostatic interactions of this type are not uncommon between RuBPY and metal oxides such as SnO 2 , TiO 2 , and SiO 2 . 83,84,112,113 Interestingly, the effect appears to be more pronounced on glass relative to FTO when taking into account the inability to produce less than 10 mm doped films on glass. This would imply a higher anionic surface charge density lending to increased localized RuDCBPY…”

Section: Table 1 Summary Of the Fluorescence Lifetime Datamentioning

confidence: 99%

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Solvothermal Growth and Photophysical Characterization of a Ruthenium(II) Tris(2,2′-Bipyridine)-Doped Zirconium UiO-67 Metal Organic Framework Thin Film

et al. 2014

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A thin film of a Ru II (bpy) 2 (dcbpy)Cl 2 , RuDCBPY, doped metal−organic framework of Zr 6 O 4 (OH) 4 (bpdc) 6 , RuDCBPY-UiO67 (where bpy is 2,2′-bipyridine, dcbpy is 5,5′-dicarboxyphenyl-2,2′-bipyridine, and bpdc is 4,4′-biphenyldicarboxylic acid), has been prepared on fluorine-doped tin oxide and glass slides solvothermally. The film is shown to be isostructural with UiO-67 and similarly doped RuDCBPY-UiO67 powders. The photophysical properties of the film show significant line broadening of the diffuse reflectance spectra, a successive red shift of the emission maxima, and biphasic kinetics with increased RuDCBPY doping of UiO-67 films above 10 mm. The two lifetime components are consistent with a dual population of RuDCBPY within the UiO-67 material: a population of RuDCBPY incorporated into the framework of UiO-67 replacing a bpdc ligand and a second population of RuDCBPY encapsulated within the octahedral cavities. The RuDCBPY dopant within the UiO-67 films interact with each other and undergo self-quenching via a resonance energy transfer mechanism. It was determined that the average distance between RuDCBPY is decreased in the film relative to similarly doped powders. This is attributed to an electrostatic effect upon formation of the framework due to increased charge at the bpdc self-assembled monolayer at the surface of the substrate. ■ INTRODUCTIONMetal−organic framework (MOF) materials continue to gain increasing attention due to their large surface areas and applicability toward catalysis, sensing, separations, and photonics. MOF engineering has, in recent years, been extended by the development of thin films, allowing for more specific/specialized applications. 1−30 The current state of the art of MOF thin film fabrication and development has recently been reviewed extensively. 31−33 Films consisting of MOFs have been prepared and grown on a variety of substrates by a number of different methods. Of the preparative methods employed to date, the most straightforward involves incubating the substrate along with the reaction mixture during the solvothermal process. 32,34−37 Solvothermal synthesis of MOF thin films has been shown to be facilitated by prior formation of a self-assembled, oriented, organic layer terminally functionalized to mimic the connectivity of one of the native MOF ligands. 32,38−40 Thin films composed of robust, stable, and porous MOFs are of particular interest in light of the harsh conditions necessary to carry out a variety of reactions and processes. The UiO (University of Oslo) series of zirconium-based materials are promising candidates owing to their exceptional stability under a variety of thermal, mechanical, and solvent conditions. 41−43 The Zr 6 O 4 (OH) 4 (COO) 6 clusters of the UiO-66, -67, and -68 frameworks arrange in such a way that two types of cavities are formed: a tetrahedral and larger octahedral cavity. 44,45 For UiO-67, in which the connecting ligand is a biphenyldicarboxylate, the diameters of the tetrahedral and octahedral pores are 11.5 and 23 Å, respe...

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Section: Resultsmentioning

confidence: 99%

Section: Table 1 Summary Of the Fluorescence Lifetime Datamentioning

confidence: 99%

Solvothermal Growth and Photophysical Characterization of a Ruthenium(II) Tris(2,2′-Bipyridine)-Doped Zirconium UiO-67 Metal Organic Framework Thin Film

et al. 2014

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“…, 1985;Wheeler and Thomas, 1982;Willner er al., 1981;Zawadzki et al, 1986). Gafney and his coworkers (Shi et al, 1985;Kennelly et al, 1985;Fan et al, 1989) those in aqueous solution. Lack of self-quenching at close to monolayer coverages indicated an absence of surface mobility of Ru(bpy)$+ in the adsorbed state.…”

Section: Introductionmentioning

confidence: 99%

Photochemistry on Surfaces. Excited State Behavior of Ruthenium Tris(bathophenanthroline Disulfonate) on Colloidal Alumina‐coated Silica Particles*

Kamat¹,

Ford²

1992

Photochem & Photobiology

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The excited state behavior of an anionic ruthenium(I1) complex, RuLj-(L = bathophenanthroline disulfonate), that is electrostatically bound to positively charged alumina-coated silica particles is investigated. The apparent association constant for the binding of RuLjto the particles is 1.2 x lo4 M-I. Surface photochemical processes result in decreased emission yields and multiexponential excited state decay. Excited state quenching by ground-state molecules is evident at high surface coverages. The non-exponential decay kinetics observed at low surface coverages can be attributed either to clustering of the RuL$-molecules or photoionization promoted by Lewis acid sites on the particle surface.

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ChemInform Abstract: Temperature Dependence of the Photoinduced Disproportionation of Ru(bpy)2+ 3 on Porous Vycor Glass.

Cited by 2 publications

References 1 publication

Solvothermal Growth and Photophysical Characterization of a Ruthenium(II) Tris(2,2′-Bipyridine)-Doped Zirconium UiO-67 Metal Organic Framework Thin Film

Solvothermal Growth and Photophysical Characterization of a Ruthenium(II) Tris(2,2′-Bipyridine)-Doped Zirconium UiO-67 Metal Organic Framework Thin Film

Photochemistry on Surfaces. Excited State Behavior of Ruthenium Tris(bathophenanthroline Disulfonate) on Colloidal Alumina‐coated Silica Particles*

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