Manipulating Spin Transition To Achieve Switchable Multifunctions

The spin transition of metal ions involves interconversion between electron configurations exhibiting considerably different functions and plays a substantial role in the chemical, physical, and biological fields. The photoinduced spin transition offers a promising approach to tune various physical properties with high spatial and temporal resolutions for producing smart multifunctional materials not only to explore their basic science but also to satisfy the demands of the next-generation photoswitchable-molecule-based devices. Therefore, it is attracting considerable interest to utilize photoinduced spin transition to simultaneously tune multifunctions. However, two issues are challenging in obtaining reversible and swift manipulation of functions: (1) the interconversion between different electron configurations of photoresponsive units should be reversibly switched via photoinduced spin transition; (2) effective coupling should be built between the photoresponsive and functional units to produce photoswitchable functions utilizing photoinduced spin transition. In this Account, we will review our recent advances in the usage of spin transition of metal ions as actuators for tuning the magnetic, dielectric, fluorescence, and mechanical properties, wherein the role of a photoswitchable spin transition is highlighted. We mainly focus on the study of two spin-transition categories, including spin-crossover (SCO) of one metal ion and metal-to-metal charge transfer (MMCT). Initially, we will describe a strategy for developing photoinduced reversible SCO and MMCT. The role of flexible intermolecular interactions, in particular, π···π interactions, is discussed with respect to a photoinduced reversible MMCT. Then, the SCO and MMCT units were assembled using metallocyanate building blocks to form a chain, wherein the spin states, anisotropy, and magnetic coupling interactions can be photoswitched to tune the single-chain magnet behavior. Besides magnetic properties, the photoinduced spin transition that is associated with the concomitant changing of charge distribution, bond lengths, and absorption spectra can be utilized to tune the multifunctions. Therefore, the transfer of an electron from a central cobalt site to one of the two iron sites in linear trinuclear Fe₂Co compounds resulted in the transformation of a centrosymmetric nonpolar molecule into an asymmetric polar molecule, and the molecular electric dipole and dielectric properties can be reversibly switched. Moreover, the spin transition usually involved significant expansion or contraction of the coordination sphere of metal ions because of the population/depopulation of the antibonding e_g orbitals. Therefore, colossal positive and negative thermal expansion behaviors were achieved in a layered compound by manipulating the spin-transition process and the rotation of the functional units, thereby providing a strategy for synthesizing phototunable nanomotors. Photoinduced spin transition can also be used to modulate the fluorescence properties by controlling the energy transfer between the fluorescent ligands and the metal sites showing SCO. Finally, we will provide a perspective and detail the remaining challenges that are associated with this research area. We believe that an increasing number of fascinating photoswitchable SCO and MMCT systems will emerge in the near future and that the materials exhibiting various properties and functions that can be manipulated using photoinduced spin transition will provide novel opportunities for the development of smart multifunctional materials and devices.