Distinct Chromic and Magnetic Properties of Metal-Organic Frameworks with a Redox Ligand

An electron-deficient and potentially chromic ligand has been utilized to impart redox activity, photo- and hydrochromism, and solvotomagnetism to metal–organic frameworks (MOFs). A pair of MOFs were constructed from the flexible zwitterionic viologen-tethered tetracarboxylate linker N,N′-bis(3,5-dicarboxylatobenzyl)-4,4′-bipyridinium (L2–): [Co3(L)(N3)4] (1) and [Mn2(L)(N3)2(H2O)2]·3H2O (2). Both compounds show three-dimensional frameworks in which mixed azido- and carboxylato-bridged chains are connected through the electron-deficient viologen moieties. The chain in 1 is built from alternating bis(azide) and (azide)bis(carboxylate) bridges, while that in 2 contains uniform (azide) (carboxylate) bridges. The MOFs shows the characteristic redox properties of the viologen moieties. The redox activity affords the MOFs with different chromic properties, owing to subtle differences in chemical environments. 1 shows reversible photochromism, which is related to the radical formation through photoinduced electr...