Spectroscopic studies of tris(2,2′-bipyridine)ruthenium(II) intercalated to modified α-zirconium phosphate

Shi, Shikao; Zhou, Ji; Zong, Ruilong; Ye, Jianping

doi:10.1016/j.jlumin.2006.01.095

Cited by 12 publications

(6 citation statements)

References 7 publications

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“…To date, RuBPY has been incorporated into a wide array of materials such as clays, − zirconium phosphate, − glasses, − and coordination polymers (e.g., zeolites ,− and metal–organic frameworks ,,,− ). For the most part, incorporation within the material has been via intercalation or encapsulation between layers or pores of the materials. ,,,,,, However, there are few examples, of which RuDCBPY-UiO-67 is one, in which modified-RuBPY has been incorporated into the material as a linker or strut, thereby comprising a portion or the whole of the material backbone. ,,,,, …”

Section: Discussionmentioning

confidence: 99%

Photophysical Characterization of a Ruthenium(II) Tris(2,2′-bipyridine)-Doped Zirconium UiO-67 Metal–Organic Framework

2014

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The photophysical properties of ruthenium(II) tris(5,5′dicarboxy-2,2′-bipyridine), RuDCBPY, doped into the metal organic framework of Zr 6 O 4 (OH) 4 (BPDC) 6 , RuDCBPY-UiO67 (where BPDC is 4,4′-biphenyldicarboxylic acid), are presented as a function of the degree of RuDCBPY doping. Steady-state diffuse reflectance of RuDCBPY-UiO67 powder shows an absorption maxima at 455 nm, which is effectively insensitive to doping concentration. The energy of the emission maxima and excited state lifetimes are, however, quite sensitive to concentration of RuDCBPY in UiO-67. At low doping concentrations, the emission maxima lies at ∼630 nm. The emission decay can be adequately modeled using a single discrete exponential decay function with an observed lifetime of 1.4 μs. The emission lifetime and the energy of the emission maxima are found to decrease with increased RuDCBPY concentration. However, at higher doping the emission decay becomes nonexponential. Equally adequate fits to the data were obtained using stretched exponential and biexponential functions. A two-state model is presented in which the nonexponential behavior observed at higher RuDCBPY doping concentrations is due to two separate solvation environments within UiO-67. It is proposed that a single RuDCBPY preferentially occupies the larger octahedral cages of UiO-67 by incorporation into the backbone of the cage and experiences a dimethylformamide (DMF)-like solvation environment. At higher doping concentrations, in addition to incorporation of RuDCBPY into the backbone of the octahedral cavities, populations of encapsulated RuDCBPY can also be found in separate octahedral UiO-67 cavities. Encapsulation is assumed to restrict the solvent occupancy within the pore; thereby limiting the solvation of RuDCBPY by DMF. This leads to the disparity in lifetimes between the slow (>100 ns) and fast (∼20−30 ns) components of the lifetime decay, as well as the lack of doping concentration dependence on the fast decay component. The decreased lifetime of the slow phase with increased doping concentration is attributed to intermolecular energy transfer between neighboring RuDCBPY molecules incorporated into the backbone of the octahedral cages.

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Section: Discussionmentioning

confidence: 99%

Photophysical Characterization of a Ruthenium(II) Tris(2,2′-bipyridine)-Doped Zirconium UiO-67 Metal–Organic Framework

2014

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“…26 28 Preparation of ZrP · 6H 2 O was carried out as indicated by Kijima with minor changes. 29 One volume of a 0.05 M ZrOCl 2 aqueous solution and one volume of a 6 M H 3 PO 4 aqueous solution were mixed and allowed to stir at 90 C for 48 h. The resulting precipitate was then filtered and washed with distilled water to obtain ZrP · 6H 2 O.…”

Section: Methodsmentioning

confidence: 99%

“…The concentration of layered material was kept constant at 0.01% (the weight percent) to minimize the interference of scattered light with the spectral measurements. 26 The quenching processes of the excited state of Ru(bpy) 2+ 3 in different surroundings were observed by photochemical oxidation of Fe(CN) 3− 6 . The aqueous solutions and assemblies suspensions of the complex (20 M) were mixed with Fe(CN) 3− 6 (the concentration changes from 1 to 5 mM) solutions and stirred for 24 h, respectively.…”

Section: Intercalation Reaction Of Ru(bpy) 2+ 3 Into the Frameworkmentioning

confidence: 99%

Enhanced Stable Luminescence and Photochemical Properties of Ruthenium Complex/Zirconium Phosphate Hybrid Assemblies

Shi¹,

Peng²,

Zhou³

2009

J. Nanosci. Nanotech.

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The luminescent metal complex Ru(bpy)3Cl2.6H2O was directly intercalated into Zr(HPO4)2.6H2O nano-lamellar framework and characterized with respect to its optical and photochemical properties. The incorporation of the complex within the inorganic framework expands the interlayer distance from 10.4 to 15.2 A, and forms complex/framework hybrid assemblies. Upon binding to the framework, the metal-to-ligand charge transfer absorption of the complex is red-shifted from 452 to 462 nm, and the maximum emission is blue-shifted from 610 to 604 nm. The luminescence intensity of the complex/framework suspensions increases more than 2-fold as compared to aqueous solutions. The sub-micrometer (0.2-0.3 microm) particles of the hybrid assemblies result in the luminescence intensity of the suspensions quite stable. In addition, the excited state of Ru(bpy)3(2+) was photochemical quenched by Fe(CN)6(3-), and the Stern-Volmer results reveal that most Ru(bpy)3(2+) cations have entered into the layer of the framework.

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“…The concentration of Zn-TMPP varied from 0.5 to 8.0 mmol L 21 , and the weight percent of OTZrP was controlled constantly at 0.01% to minimize the interference of scattered light with spectral measurements. 30 The above suspensions were continually agitated for over 24 h at ambient temperature to ensure a thorough intercalation reaction.…”

Section: Intercalation Reactionmentioning

confidence: 99%

Fabrication and spectroscopic properties of a metalloporphyrin-intercalated zirconium phosphate assembly

et al. 2013

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Spectroscopic studies of tris(2,2′-bipyridine)ruthenium(II) intercalated to modified α-zirconium phosphate

Cited by 12 publications

References 7 publications

Photophysical Characterization of a Ruthenium(II) Tris(2,2′-bipyridine)-Doped Zirconium UiO-67 Metal–Organic Framework

Photophysical Characterization of a Ruthenium(II) Tris(2,2′-bipyridine)-Doped Zirconium UiO-67 Metal–Organic Framework

Enhanced Stable Luminescence and Photochemical Properties of Ruthenium Complex/Zirconium Phosphate Hybrid Assemblies

Fabrication and spectroscopic properties of a metalloporphyrin-intercalated zirconium phosphate assembly

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