Zeolite host-guest interactions:  optical spectroscopic properties of tris(bipyridine)ruthenium(II) in zeolite Y cages

Incavo, Joseph A.; Dutta, Prabir K.

doi:10.1021/j100370a061

Cited by 100 publications

(64 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Raman spectroscopy of [Fe(bpy) 3 ] 2+ and [Ru(bpy) 3 ] 2+ separately encapsulated in zeolite have been reported previously. 37,38 Figure 3a shows the resonance Raman spectrum of solid [Fe-(tpy) 2 ][PF 6 ] 2 excited at 457.9 nm, and Figure 3b shows the spectrum for Z-[Fe(tpy) 2 ] 2+ under the same conditions. This excitation wavelength is pre-resonant with the MLCT transition, and therefore, modes associated with chromophores involved with this transition are enhanced.…”

Section: Resultsmentioning

confidence: 99%

Influence of Steric Confinement within Zeolite Y on Photoinduced Energy Transfer between [Ru(bpy)₃]²⁺ and Iron Polypyridyl Complexes

2008

View full text Add to dashboard Cite

The spectroscopic and photophysical properties of zeolite-Y-entrapped [Ru(bpy)3]2+ co-doped with either [Fe(bpy)3]2+ or [Fe(tpy)2]2+ over a range of iron complex loadings are presented. In solution, [Ru(bpy)3]2+ undergoes efficient bimolecular energy transfer to [Fe(bpy)3]2+, whereas only radiative or trivial energy transfer occurs between [Ru(bpy)3]2+ and [Fe(tpy)2]2+. In sharp contrast, within zeolite Y, both [Fe(bpy)3]2+ and [Fe(tpy)2]2+ were found to effectively quench the donor emission. Fitting the Perrin model to the photophysical data yields an effective quenching radius of 32 and 27 A, respectively, for [Fe(bpy)3]2+ and [Fe(tpy)2]2+. The long-range nature of the quenching suggests Förster energy transfer. Detailed spectroscopic investigations indicate that [Fe(tpy)2]2+ bound within zeolite Y undergoes significant distortion from octahedral geometry. This distortion results in increased oscillator strength and enhanced spectral overlap, between the [Ru(bpy)3]2+ (3)d pi-pi* donor emission and the co-incident acceptor (1)T2-(1)A1 ligand field absorption compared with solution. This turns on an efficient energy transfer to [Fe(tpy)2]2+ within the confinement of the zeolite Y supercage. Overall, this is an interesting example of the ability of the zeolite environment to provoke new photophysical processes not possible in solution.

show abstract

Section: Resultsmentioning

confidence: 99%

Influence of Steric Confinement within Zeolite Y on Photoinduced Energy Transfer between [Ru(bpy)₃]²⁺ and Iron Polypyridyl Complexes

2008

View full text Add to dashboard Cite

show abstract

“…27 Luminescence quenching experiments have implicated static quenching by water molecules wedged between the bpy ligands, 26 and Raman studies of [Ru(bpy) 3 ] 2C lodged in zeolite cavities have shown that overall intensities are perturbed by hydration even though the cavity radius is only slightly larger than that of the complex. 28 The luminescence yield of [Ru(bpy) 3 ] 2C is lower in H 2 O than in D 2 O, 29,30 but approximately independent of solvent isotope in acetonitrile. Taken with the resonance Raman intensities observed in this work, it is clear that excited-state dynamics of [Ru(bpy) 3 ] 2C are very different in water and acetonitrile.…”

Section: Discussionmentioning

confidence: 99%

Resonance Raman spectrum of [Ru(bipyridine)₃]²⁺ in water, acetonitrile and their deuterated derivatives: the possible role of solvent in excited‐state charge localization

Webb

Knorr

McHale

2001

J Raman Spectroscopy

View full text Add to dashboard Cite

Resonance Raman spectra excited at 458 and 476 nm are reported for [Ru(bipyridine) 3 ] 2+ in water, acetonitrile and their perdeuterated derivatives. Raman intensities of [Ru(bipyridine) 3 ] 2+ are about a factor of two greater in H 2 O than D 2 O for all vibrational modes, but are independent of solvent isotopomer in acetonitrile. Solvent dynamics apparently contribute more strongly to the dephasing dynamics in water than in acetonitrile. Mode-specific dephasing rates seem to cause different depolarization ratios for different observed vibrations which can lead to a potentially misleading interpretation of the depolarization ratios. We speculate that a static complex between [Ru(bipyridine) 3 ] 2+ and water influences the excited-state dynamics.

show abstract

“…The assembly of donor-acceptor pairs in heterogeneous support systems, such as zeolites, clays, and polymers, can provide the appropriate electrostatic and steric environment for the prevention of BeT, thereby favoring the generation of a long-lived charge-separated state. The study of zeolites as supramolecular scaffolds for energy storage systems (via long-lived charge separation) has been pioneered largely by Dutta et al [14,15,[73][74][75][76][77][78] with significant contributions also from the groups of Kincaid [79,80] and Mallouk [81][82][83]. There are many examples demonstrating how intelligent use of the zeolite framework, to spatially organize the donor and acceptor components, can result in the generation of extremely long-lived charge-separated states.…”

Section: Electron Transfermentioning

confidence: 99%

Supramolecular photochemistry in zeolites: From catalysts to sunscreens

Chrétien

2007

Pure and Applied Chemistry

View full text Add to dashboard Cite

Zeolites are nanoporous, crystalline aluminosilicate materials comprised of a series of strictly uniform channels and cavities repeating along the tri-directional structure of the lattice. Over the last 30 years, researchers have increasingly recognized the desirable properties of these materials as hosts for photochemical reactions. This review will endeavor to draw attention to the properties of zeolite materials that make them appealing substrates for hosting guest molecules during photochemical reactions. An overview of some classical examples in zeolite host-guest photochemistry will be presented along with a brief description of a new use for zeolite materials as protective encapsulators.

show abstract

Zeolite host-guest interactions: optical spectroscopic properties of tris(bipyridine)ruthenium(II) in zeolite Y cages

Cited by 100 publications

References 0 publications

Influence of Steric Confinement within Zeolite Y on Photoinduced Energy Transfer between [Ru(bpy)₃]²⁺ and Iron Polypyridyl Complexes

Influence of Steric Confinement within Zeolite Y on Photoinduced Energy Transfer between [Ru(bpy)₃]²⁺ and Iron Polypyridyl Complexes

Resonance Raman spectrum of [Ru(bipyridine)₃]²⁺ in water, acetonitrile and their deuterated derivatives: the possible role of solvent in excited‐state charge localization

Supramolecular photochemistry in zeolites: From catalysts to sunscreens

Contact Info

Product

Resources

About

Zeolite host-guest interactions: optical spectroscopic properties of tris(bipyridine)ruthenium(II) in zeolite Y cages

Cited by 100 publications

References 0 publications

Influence of Steric Confinement within Zeolite Y on Photoinduced Energy Transfer between [Ru(bpy)3]2+ and Iron Polypyridyl Complexes

Influence of Steric Confinement within Zeolite Y on Photoinduced Energy Transfer between [Ru(bpy)3]2+ and Iron Polypyridyl Complexes

Resonance Raman spectrum of [Ru(bipyridine)3]2+ in water, acetonitrile and their deuterated derivatives: the possible role of solvent in excited‐state charge localization

Supramolecular photochemistry in zeolites: From catalysts to sunscreens

Contact Info

Product

Resources

About

Influence of Steric Confinement within Zeolite Y on Photoinduced Energy Transfer between [Ru(bpy)₃]²⁺ and Iron Polypyridyl Complexes

Influence of Steric Confinement within Zeolite Y on Photoinduced Energy Transfer between [Ru(bpy)₃]²⁺ and Iron Polypyridyl Complexes

Resonance Raman spectrum of [Ru(bipyridine)₃]²⁺ in water, acetonitrile and their deuterated derivatives: the possible role of solvent in excited‐state charge localization