The Advent of Electrically Conducting Double-Helical Metal-Organic Frameworks Featuring Butterfly-Shaped Electron-Rich π-Extended Tetrathiafulvalene Ligands.

To diversify metal-organic framework (MOF) structures beyond traditional Euclidean geometries and to create new charge-delocalization pathways beneficial for electrical conductivity, we constructed a novel double-helical MOF (dhMOF) by introducing a new butterfly-shaped electron-rich π-extended tetrathiafulvalene ligand equipped with four benzoate groups (ExTTFTB). The face-to-face oriented convex ExTTFTB ligands connected by Zn2(COO)4 paddlewheel nodes formed ovoid cavities suitable for guest encapsulation, while π-π-interaction between the ExTTFTB ligands of neighboring strands helped create new charge-delocalization pathways in iodine-mediated partially oxidized dhMOF. Iodine vapor diffusion led to oxidation of half of the ExTTFTB ligands in each double-helical strand to ExTTFTB•+ radical cations, which putatively formed intermolecular ExTTFTB/ExTTFTB•+ π-donor/acceptor charge-transfer chains with the neutral ExTTFTB ligands of an adjacent strand, creating supramolecular wire-like charge-delocalization pathways along the helix seams. In consequence, the electrical conductivity of dhMOF surged from 10-8 S/m up to 10-4 S/m range after iodine treatment. Thus, the introduction of the electron-rich ExTTFTB ligand with a distinctly convex π-surface not only afforded a novel double-helical MOF architecture featuring ovoid cavities and unique charge-delocalization pathways but also, more importantly, delivered a new tool and design strategy for future development of electrically conducting stimuli-responsive MOFs.