Metal-organic frameworks (MOFs) are a new class of nanoporous materials in which metal cations coordinated to groups such as carboxylates and aromatic amines create a semi-rigid supramolecular structure. The tailorable geometry and chemical environment of MOF pores makes them attractive for sensing applications, and both chemical and radiation detection using luminescent MOFs have been demonstrated. However, the relationship between MOF structure and luminescent properties is not well understood. We will discuss results demonstrating that MOF luminescence is governed by interactions at all levels: primary (individual chromophores), secondary (between chromophores within a pore), and tertiary (between chromophores in neighboring interpenetrated lattices). Luminescence data suggest there is minimal charge transfer in MOFs composed of Zn(II) and carboxylate linkers; however, interchromophore orientation strongly affects both the spectrum and excited-state lifetime. MOFs possess a fourth relevant �dimension� resulting from reversible adsorbate-induced structural modifications, creating potential for selective detection of acceptor molecules within the pores.

Charge transfer in metal-organic frameworks: Implications for sensing

243rd National Meeting (2012)

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