Incorporating Electron-Deficient Bipyridinium Chromorphores to Make Multiresponsive Metal–organic Frameworks

Abstract

Metal-organic frameworks (MOFs) are versatile platforms to design switchable and sensory materials responsive to external stimulus. Copuling the electron-deficient bipyridinium chromorphore with the pore structures of MOFs is a nice strategy to design multiresponsive MOFs. Here we present a proof-of-concept study. Postsynthetic N,N'-cycloalkylation of UiO-67-bpy (bpy = 2,2'-bipyridyl) leads to a novel ionic MOF (UiO-67-DQ) functionalized by the electron-deficient diquat (DQ) chromophore. The combination of porosity, cationic character and electron deficiency imparts UiO-67-DQ with versatile responsive properties. It readily undergoes anion exchange, with selective ionochromism associated with charge-transfer (CT) complexation; it is electrochemically active and shows anion-dependent photochromism associated with radical formation through electron transfer (ET); the iono- and photochromism cause efficient luminescence quenching because of energy transfer (EnT) to CT complexes or radicals. The properties of UiO-67-MQ (MQ = N,N'-dimethyl-2,2'-bipyridylium) are also presented for comparison. The CT and ET effects and consequently the EnT efficiency in UiO-67-MQ are weaker than those in UiO-67-DQ because the electron-deficient character is weakened by the severe interannular twist in MQ²⁺. On the basis of the rich responsive properties, the MOFs are used as sensory and switching materials for facile discrimination of a range of anions, for quantitative detection of I^-, and for mimicking of logic operations ranging from simple logic gates to complex integrated logic circuits.