Versatile and Switchable Responsive Properties of a Lanthanide-Viologen Metal-Organic Framework.

Abstract

Metal-organic frameworks (MOFs) provide intriguing platforms for the design of responsive materials. It is challenging to mobilize as many components as possible of a MOF to collaboratively accomplish multiple responsive properties. Here, reversible photochromism, piezochromism, hydrochromism, ionochromism, and luminescence modulation of an ionic Eu(III) MOF is reported furnished by cationic electron-deficient viologen units and exchangeable guest anions. Mechanistically, the extraordinarily versatile responsive properties are owed to electron transfer (ET), charge transfer (CT), and energy transfer, involving viologen as electron acceptor, anion as electron donor, luminescing Eu(III) as energy donor, and anion-viologen CT complex or ET-generated radical as energy acceptor (luminescence quencher). Moreover, guest anions and waters provide flexible handles to control the ET-based responsive properties. Water release/reuptake or exchange with organic solvents can switch on/off the response to light, while reversible anion exchange can disenable or awaken the responses to pressure, light, and water release/reuptake. The impacts of water and anions on ET are justified by the high polarity and hydrogen-bonding capability of water, the different electron donor strength of anions, and the strong I- -viologen CT interactions. The rich responsive behaviors have great implications for applications such as pressure sensors, iodide detection, and chemical logic gates.