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Title: Photophysical properties of [Ru(2,2′-bipyridine){sub 3}]{sup 2+} encapsulated within the Uio-66 zirconium based metal organic framework

Abstract

The ability to encapsulate photo-active guest molecules within the pores of metal organic frameworks (MOFs) affords the opportunity to develop robust photocatalysts as well as solar energy conversion systems. An important criteria for such systems is stability of the new materials towards moisture, high temperatures, etc which preclude the use of many MOF frameworks. Here, the ability to encapsulate [Ru(II)(2,2′-bipyridine){sub 3}]{sup 2+}([Ru(bpy){sub 3}]{sup 2+}) into the cavities of the zirconium based MOF Uio-66 as well as the photophysical properties of the complex are reported. The X-ray powder diffraction data of the orange Uio-66 powder are consistent with the formation of Uio-66 in the presence of [Ru(bpy){sub 3}]{sup 2+}. The steady state emission exhibits a significant bathochromic shift from 603 nm in ethanol to 610 nm in Uio-66. The corresponding emission decay of the encapsulated [Ru(bpy){sub 3}]{sup 2+} complex is biexponential with a fast component of 128 ns and a slower component of 1176 ns (20 deg C). The slow component is consistent with encapsulation of [Ru(bpy){sub 3}]{sup 2+} into cavities with restricted volume that prevents the population of a triplet ligand field transition that is anti-bonding with respect to the Ru-N bonds. The origin of the fast component is unclearmore » but may involve interactions of the [Ru(bpy){sub 3}]{sup 2+} encapsulated within large cavities formed through missing ligand defect sites within the Uio-66 materials. Co-encapsulated quenchers contained within these larger cavities gives rise to the reduced lifetimes of the [Ru(bpy){sub 3}]{sup 2+} complexes. - Graphical abstract: One-pot synthesis of Ru(II)tris(2,2-bipyridine)@Uio-66 (left) and the effects of encapsulation on the excited state energy levels and decay pathways of the Ru(II)tris(2,2-bipyridine) complex (right).« less

Authors:
;
Publication Date:
OSTI Identifier:
22658221
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 247; Other Information: Copyright (c) 2017 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CAVITIES; COMPLEXES; ENCAPSULATION; EXCITED STATES; ORGANOMETALLIC COMPOUNDS; PYRIDINES; RUTHENIUM COMPOUNDS; SOLAR ENERGY CONVERSION; TEMPERATURE RANGE 0400-1000 K; X-RAY DIFFRACTION; ZIRCONIUM

Citation Formats

Larsen, Randy W., E-mail: rwlarsen@usf.edu, and Wojtas, Lukasz. Photophysical properties of [Ru(2,2′-bipyridine){sub 3}]{sup 2+} encapsulated within the Uio-66 zirconium based metal organic framework. United States: N. p., 2017. Web. doi:10.1016/J.JSSC.2016.12.028.
Larsen, Randy W., E-mail: rwlarsen@usf.edu, & Wojtas, Lukasz. Photophysical properties of [Ru(2,2′-bipyridine){sub 3}]{sup 2+} encapsulated within the Uio-66 zirconium based metal organic framework. United States. doi:10.1016/J.JSSC.2016.12.028.
Larsen, Randy W., E-mail: rwlarsen@usf.edu, and Wojtas, Lukasz. Wed . "Photophysical properties of [Ru(2,2′-bipyridine){sub 3}]{sup 2+} encapsulated within the Uio-66 zirconium based metal organic framework". United States. doi:10.1016/J.JSSC.2016.12.028.
@article{osti_22658221,
title = {Photophysical properties of [Ru(2,2′-bipyridine){sub 3}]{sup 2+} encapsulated within the Uio-66 zirconium based metal organic framework},
author = {Larsen, Randy W., E-mail: rwlarsen@usf.edu and Wojtas, Lukasz},
abstractNote = {The ability to encapsulate photo-active guest molecules within the pores of metal organic frameworks (MOFs) affords the opportunity to develop robust photocatalysts as well as solar energy conversion systems. An important criteria for such systems is stability of the new materials towards moisture, high temperatures, etc which preclude the use of many MOF frameworks. Here, the ability to encapsulate [Ru(II)(2,2′-bipyridine){sub 3}]{sup 2+}([Ru(bpy){sub 3}]{sup 2+}) into the cavities of the zirconium based MOF Uio-66 as well as the photophysical properties of the complex are reported. The X-ray powder diffraction data of the orange Uio-66 powder are consistent with the formation of Uio-66 in the presence of [Ru(bpy){sub 3}]{sup 2+}. The steady state emission exhibits a significant bathochromic shift from 603 nm in ethanol to 610 nm in Uio-66. The corresponding emission decay of the encapsulated [Ru(bpy){sub 3}]{sup 2+} complex is biexponential with a fast component of 128 ns and a slower component of 1176 ns (20 deg C). The slow component is consistent with encapsulation of [Ru(bpy){sub 3}]{sup 2+} into cavities with restricted volume that prevents the population of a triplet ligand field transition that is anti-bonding with respect to the Ru-N bonds. The origin of the fast component is unclear but may involve interactions of the [Ru(bpy){sub 3}]{sup 2+} encapsulated within large cavities formed through missing ligand defect sites within the Uio-66 materials. Co-encapsulated quenchers contained within these larger cavities gives rise to the reduced lifetimes of the [Ru(bpy){sub 3}]{sup 2+} complexes. - Graphical abstract: One-pot synthesis of Ru(II)tris(2,2-bipyridine)@Uio-66 (left) and the effects of encapsulation on the excited state energy levels and decay pathways of the Ru(II)tris(2,2-bipyridine) complex (right).},
doi = {10.1016/J.JSSC.2016.12.028},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 247,
place = {United States},
year = {Wed Mar 15 00:00:00 EDT 2017},
month = {Wed Mar 15 00:00:00 EDT 2017}
}