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Issue 37, 2017
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A novel photo-active Cd:1,4-benzene dicarboxylate metal organic framework templated using [Ru(II)(2,2′-bipyridine)3]2+: synthesis and photophysics of RWLC-5

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Abstract

The development of photoactive porous materials is of significant importance for applications ranging from sustainable energy to pharmaceutical development and catalysis. A particularly attractive class of photo-active materials is the metal–organic framework (MOF)-based platform in which the photo-active elements are components of the framework itself or photo-active guests encapsulated within the MOF cavities. It has now been demonstrated that the photo-active [Ru(2,2′-bipyridine)3]2+ (RuBpy) complex can template the formation of MOFs with varying three dimensional structures. Here we report the synthesis and structural and photo-physical characterization of a new RuBpy-templated MOF composed of Cd2+ ions with 1,4-benzenedicarboxylate ligands (RWLC-5) that contains crystallographically resolved RuBpy complexes. The new material displays a biphasic emission decay (130 ns and 1180 ns, T = 20 °C) and a bathochromically shifted emission maximum, relative to RuBpy in solution (603 nm for RuBpy in ethanol vs. 630 nm for RWLC-5). The emission lifetimes also do not display temperature-dependent decays which are characteristic of RuBpy type complexes as well as other RuBpy templated MOFs. The lack of temperature dependence is consistent with the complete deactivation of the 3LF state of the encapsulated RuBpy complex due to a constrained environment. The fast phase decay is attributed to a water molecule hydrogen bonded to a bipyridine ligand associated with ∼38% of the encapsulated RuBpy complexes resulting in the nonradiative deactivation of the 3MLCT state.

Graphical abstract: A novel photo-active Cd:1,4-benzene dicarboxylate metal organic framework templated using [Ru(ii)(2,2′-bipyridine)3]2+: synthesis and photophysics of RWLC-5

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Publication details

The article was received on 05 Jul 2017, accepted on 15 Aug 2017 and first published on 18 Aug 2017


Article type: Paper
DOI: 10.1039/C7DT02436C
Citation: Dalton Trans., 2017,46, 12711-12716
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    A novel photo-active Cd:1,4-benzene dicarboxylate metal organic framework templated using [Ru(II)(2,2′-bipyridine)3]2+: synthesis and photophysics of RWLC-5

    R. W. Larsen, J. M. Mayers and L. Wojtas, Dalton Trans., 2017, 46, 12711
    DOI: 10.1039/C7DT02436C

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