Search for: All records

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.

 

We report a metal–organic framework (MOF) with a rare two‐dimensional (2D) secondary building unit (SBU). The SBU comprises mixed‐valent Fe²⁺and Fe³⁺metal ions bridged by oxygen atoms pertaining to the polytopic ligand 3,3′,4,4′,5,5′‐hexahydroxybiphenyl, which also define the iron‐oxide 2D layers. Overall, the anionic framework exhibits rare topology and evidences strong electronic communication between the mixed‐valence iron sites. These results highlight the importance of dimensionality control of MOF SBUs for discovering new topologies in reticular chemistry, and especially for improving electronic communication within the MOF skeleton.

 

Metal–organic frameworks (MOFs) are hybrid materials known for their nanoscale pores, which give them high surface areas but generally lead to poor electrical conductivity. Recently, MOFs with high electrical conductivity were established as promising materials for a variety of applications in energy storage and catalysis. Many recent reports investigating the fundamentals of charge transport in these materials focus on the role of the organic ligands. Less consideration, however, is given to the metal ion forming the MOF, which is almost exclusively a late first‐row transition metal. Here, we report a moderately conductive porous MOF based on trivalent gallium and 2,3,6,7,10,11‐hexahydroxytriphenylene. Gallium, a metal that has not been featured in electrically conductive MOFs so far, has a closed‐shell electronic configuration and is present in its trivalent state—in contrast to most conductive MOFs, which are formed by open‐shell, divalent transition metals. Our material, made without using any harmful solvents, displays conductivities on the level of 3 mS/cm and a surface area of 196 m²/g, comparable to transition metal analogs.

 

Phosphane, PH₃—a highly pyrophoric and toxic gas—is frequently contaminated with H₂and P₂H₄, which makes its handling even more dangerous. The inexpensive metal–organic framework (MOF) magnesium formate, α‐[Mg(O₂CH)₂], can adsorb up to 10 wt % of PH₃. The PH₃‐loaded MOF, PH₃@α‐[Mg(O₂CH)₂], is a non‐pyrophoric, recoverable material that even allows brief handling in air, thereby minimizing the hazards associated with the handling and transport of phosphane. α‐[Mg(O₂CH)₂] further plays a critical role in purifying PH₃from H₂and P₂H₄: at 25 °C, H₂passes through the MOF channels without adsorption, whereas PH₃adsorbs readily and only slowly desorbs under a flow of inert gas (complete desorption time≈6 h). Diphosphane, P₂H₄, is strongly adsorbed and trapped within the MOF for at least 4 months. P₂H₄@α‐[Mg(O₂CH)₂] itself is not pyrophoric and is air‐ and light‐stable at room temperature.

 

Selectively blocking undesirable exciton transfer pathways is crucial for utilizing exciton conversion processes that involve participation of multiple chromophores. This is particularly challenging for solid-state systems, where the chromophores are fixed in close proximity. For instance, the low efficiency of solid-state triplet–triplet upconversion calls for inhibiting the parasitic singlet back-transfer without blocking the flow of triplet excitons. Here, we present a reticular chemistry strategy that inhibits the resonance energy transfer of singlet excitons. Within a pillared layer metal–organic framework (MOF), pyrene-based singlet donors are situated perpendicular to porphyrin-based acceptors. High resolution transmission electron microscopy and electron diffraction enable direct visualization of the structural relationship between donor and acceptor (D–A) chromophores within the MOF. Time-resolved photoluminescence measurements reveal that the structural and symmetry features of the MOF reduce the donor-to-acceptor singlet transfer efficiency to less than 36% compared to around 96% in the control sample, where the relative orientation of the donor and acceptor chromophores cannot be controlled.