Reversible structural transformations of porous coordination frameworks in response to external stimuli such as light, electrical potential, guest inclusion or pressure, amongst others, have been the subject of intense interest for applications in sensing, switching and molecular separations. Here we report a coordination framework based on an electroactive tetrathiafulvalene exhibiting a reversible single crystal-to-single crystal double [2 + 2] photocyclisation, leading to profound differences in the electrochemical, optical and mechanical properties of the material upon light irradiation. Electrochemical and in situ spectroelectrochemical measurements, in combination with in situ light-irradiated Raman spectroscopy and atomic force microscopy, revealed the variable mechanical properties of the framework that were supported using Density Functional Theory calculations. The reversible structural transformation points towards a plethora of potential applications for coordination frameworks in photo-mechanical and photoelectrochemical devices, such as light-driven actuators and photo-valves for targeted drug delivery.

Electroactive and conducting framework materials, encompassing coordination polymers and metal–organic frameworks, have captured the imagination of the scientific community owing to their highly designable nanoporous structures and their potential applications in electrochromic devices, electrocatalysts, porous conductors, batteries and solar energy harvesting systems, among many others. While they are now considered integral members of the broader field of inorganic materials, it is timely to reflect upon their strengths and challenges compared with ‘traditional’ solid-state materials such as minerals, pigments and zeolites. Indeed, the latter have been known since ancient times and have been prized for centuries in fields as diverse as art, archaeology and industrial catalysis. This opinion piece considers a brief historical perspective of traditional electroactive and conducting inorganic materials, with a view towards very recent experimental progress and new directions for future progress in the burgeoning area of coordination polymers and metal–organic frameworks. Overall, this article bears testament to the rich history of electroactive solids and looks at the challenges inspiring a new generation of scientists. This article is part of the theme issue ‘Mineralomimesis: natural and synthetic frameworks in science and technology’.

Metal–organic frameworks (MOFs) provide broad prospects for the development of new photothermal conversion materials, while their design and synthesis remain challenging. A new Zn-MOF (1) containing both tetrathiafulvalene (TTF) as an electron donor and naphthalene diimide (NDI) as an electron acceptor was constructed by using a space limiting effect. The material exhibited wide absorption peaks in the near-infrared region, indicating that there was strong charge transfer interaction between the TTF and NDI units and providing the possibility of photothermal conversion. 1 shows efficient near-infrared photothermal conversion performance. Under 808 nm laser (0.4 W cm–2) illumination, the temperature of 1 increased rapidly from room temperature to 250 °C, with good thermal stability and cycle durability. This work provides an efficient strategy for promising materials in photothermal therapy.