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

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posted on 02.08.2012, 00:00 authored by Randy W. Larsen, Lukasz Wojtas
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.