Partial oxidation of an iron-tetrazolate metal-organic framework (MOF) upon exposure to ambient atmosphere yields a mixed-valence material with single-crystal conductivities tunable over 5 orders of magnitude and exceeding 1 S/cm, the highest for a three-dimensionally connected MOF. Variable-temperature conductivity measurements reveal a small activation energy of 160 meV. Electronic spectroscopy indicates the population of midgap states upon air exposure and corroborates intervalence charge transfer between Fe and Fe centers. These findings are consistent with low-lying Fe defect states predicted by electronic band structure calculations and demonstrate that inducing metal-based mixed valency is a powerful strategy toward realizing high and systematically tunable electrical conductivity in MOFs.
Identifying the metal ions that optimize charge transport and charge density in metal–organic frameworks is critical for systematic improvements in the electrical conductivity in these materials.
The use of two-dimensional (2D) materials in nextgeneration technologies is often limited by small lateral size and/or crystal defects. Here, we introduce a simple chemical strategy to improve the size and overall quality of 2D metal−organic chalcogenolates (MOCs), a new class of hybrid organic−inorganic 2D semiconductors that can exhibit in-plane anisotropy and blue luminescence. By inducing the formation of silver−amine complexes during a solution growth method, we increase the average size of silver phenylselenolate (AgSePh) microcrystals from <5 μm to >1 mm, while simultaneously extending the photoluminescence lifetime and suppressing mid-gap emission. Mechanistic studies using 77 Se NMR suggest dual roles for the amine in promoting the formation of a key reactive intermediate and slowing down the final conversion to AgSePh. Finally, we show that amine addition is generalizable to the synthesis of other 2D MOCs, as demonstrated by the growth of single crystals of silver 4-methylphenylselenolate (AgSePhMe), a novel member of the 2D MOC family.
Triplet-fusion-based photon upconversion holds promise for a wide range of applications, from photovoltaics to bioimaging. The efficiency of triplet fusion, however, is fundamentally limited in conventional molecular and polymeric systems by its spin dependence. Here, we show that the inherent tailorability of metal–organic frameworks (MOFs), combined with their highly porous but ordered structure, minimizes intertriplet exchange coupling and engineers effective spin mixing between singlet and quintet triplet–triplet pair states. We demonstrate singlet–quintet coupling in a pyrene-based MOF, NU-1000. An anomalous magnetic field effect is observed from NU-1000 corresponding to an induced resonance between singlet and quintet states that yields an increased fusion rate at room temperature under a relatively low applied magnetic field of 0.14 T. Our results suggest that MOFs offer particular promise for engineering the spin dynamics of multiexcitonic processes and improving their upconversion performance.
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