Toroidal moment and dynamical control in luminescent 1D and 3D terbium calixarene compounds

A toroidal moment can be generated spontaneously in inorganic (atom-based) ferrotoroidic materials that breaks both time-reversal and space-inversion symmetries, attracting great attention in solid-state chemistry and physics. In the field of molecular magnetism, it can also be achieved in lanthanide (Ln) involved metal–organic complexes usually with a wheel-shaped topological structure. Such complexes are called single-molecule toroics (SMTs), presenting unique advantages in spin chirality qubits and magnetoelectric coupling. However, to date, the synthetic strategies of SMTs have remained elusive, and the covalently bonded three-dimensional (3D) extended SMT has not hitherto been synthesized. Here, two luminescent Tb(iii)–calixarene aggregates with architectures of 1D chain (1) and 3D network (2) both containing the square Tb(4) unit have been prepared. Their SMT characteristics deriving from the toroidal arrangement of the local magnetic anisotropy axes of Tb(iii) ions in the Tb(4) unit have been investigated experimentally with the support of ab initio calculations. To the best of our knowledge, 2 is the first covalently bonded 3D SMT polymer. Remarkably, solvato-switching of SMT behavior has also been achieved for the first time by desolvation and solvation processes of 1.