Ruthenium(II) Tris(2,2′-bipyridine)-Templated Zinc(II) 1,3,5-Tris(4-carboxyphenyl)benzene Metal Organic Frameworks: Structural Characterization and Photophysical Properties

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, two new Ru(II) tris(2,2'-bipyridine) (RuBpy)-based photoactive materials derived from reactions between Zn(II) ions and 1,3,5-tris(4-carboxyphenyl)benzene and templated by the presence of RuBpy (RWLC-1 and RWLC-2) are described with regard to structure and RuBpy photophysics. RuBpy cations have been successfully encapsulated within the cavities (RWLC-1) and channels (RWLC-2) of the new negatively charged frameworks, both of which are synthesized simultaneously in a single reaction vial. Single-crystal X-ray diffraction studies allowed for determination of the RuBpy position within crystal voids. RuBpy encapsulated in each of the two new MOFs exhibits biphasic triplet metal to ligand charge transfer ((3)MLCT) emission decay lifetimes (τRWLC-1-fast = 237 ns, τRWLC-1-slow = 1.60 μs, τRWLC-2-fast = 171 ns, and τRWLC-2-slow = 797 ns at 25 °C) consistent with two populations of RuBpy complexes, one being encapsulated in highly space-restricted cavities giving rise to a longer (3)MLCT lifetime, while the second is encapsulation within a larger nonperiodic pore or defect with a coencapsulated quencher giving rise to short emission lifetimes. Taken together, these results represent examples of the templating ability of RuBpy to produce novel materials with distinct photophysical environments of the encapsulated guests.