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Title: Photophysical Studies of Ru(II)tris(2,2`-bipyridine) Confined within a Zn(II)-Trimesic Acid Polyhedral Metal-Organic Framework

Abstract

The ability to confine photoactive catalysts within metal-organic framework (MOF) materials affords the opportunity to expand the functional diversity of these materials into solar based applications. Here, the confinement of Ru(II)tris(2,2'-bipyridine) (RuBpy) by a MOF material derived from Zn(II) ions and trimesic acid (hereafter, USF2) is examined. Although the encapsulated RuBpy could not be crystallographically resolved within the MOF framework, the photophysical properties of the complex are characteristic of confinement including extended triplet metal-to-ligand ( 3MLCT) lifetime (τ ethanol = 614 ns and {τ USF2 = 1.2 μs at 25 °C) and a slight hypsochromic shift in the steady-state emission spectrum relative to RuBpy in ethanol. The extended lifetime is attributed to a deactivation of a nonradiative 3dd that is antibonding with respect to the Ru(II)-bipyridine due to a confined molecular environment. These results represent one of the first examples of RuBpy encapsulation and photophysical characterization within a polyhedral MOF material.

Authors:
;  [1]
  1. USF
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States). Advanced Photon Source (APS)
Sponsoring Org.:
NSFDOE - BASIC ENERGY SCIENCES
OSTI Identifier:
1047890
Resource Type:
Journal Article
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
Journal Volume: 116; Journal Issue: (30) ; 08, 2012; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
ENGLISH
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CATALYSTS; CONFINEMENT; DEACTIVATION; ENCAPSULATION; ETHANOL; FUNCTIONALS; LIFETIME; TRIPLETS

Citation Formats

Larsen, Randy W, and Wojtas, Lukasz. Photophysical Studies of Ru(II)tris(2,2`-bipyridine) Confined within a Zn(II)-Trimesic Acid Polyhedral Metal-Organic Framework. United States: N. p., 2012. Web. doi:10.1021/jp302979a.
Larsen, Randy W, & Wojtas, Lukasz. Photophysical Studies of Ru(II)tris(2,2`-bipyridine) Confined within a Zn(II)-Trimesic Acid Polyhedral Metal-Organic Framework. United States. doi:10.1021/jp302979a.
Larsen, Randy W, and Wojtas, Lukasz. Thu . "Photophysical Studies of Ru(II)tris(2,2`-bipyridine) Confined within a Zn(II)-Trimesic Acid Polyhedral Metal-Organic Framework". United States. doi:10.1021/jp302979a.
@article{osti_1047890,
title = {Photophysical Studies of Ru(II)tris(2,2`-bipyridine) Confined within a Zn(II)-Trimesic Acid Polyhedral Metal-Organic Framework},
author = {Larsen, Randy W and Wojtas, Lukasz},
abstractNote = {The ability to confine photoactive catalysts within metal-organic framework (MOF) materials affords the opportunity to expand the functional diversity of these materials into solar based applications. Here, the confinement of Ru(II)tris(2,2'-bipyridine) (RuBpy) by a MOF material derived from Zn(II) ions and trimesic acid (hereafter, USF2) is examined. Although the encapsulated RuBpy could not be crystallographically resolved within the MOF framework, the photophysical properties of the complex are characteristic of confinement including extended triplet metal-to-ligand (3MLCT) lifetime (τethanol = 614 ns and {τUSF2 = 1.2 μs at 25 °C) and a slight hypsochromic shift in the steady-state emission spectrum relative to RuBpy in ethanol. The extended lifetime is attributed to a deactivation of a nonradiative 3dd that is antibonding with respect to the Ru(II)-bipyridine due to a confined molecular environment. These results represent one of the first examples of RuBpy encapsulation and photophysical characterization within a polyhedral MOF material.},
doi = {10.1021/jp302979a},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
issn = {1089-5639},
number = (30) ; 08, 2012,
volume = 116,
place = {United States},
year = {2012},
month = {10}
}