Such exciting properties as porosity and single-ion magnetic behavior are merged into a single unique material which affords the first in-depth study of guest-dependent SIM behavior in a MOF.

A vast impact on molecular nanoscience can be achieved using simple transition metal complexes as dynamic chemical systems to perform specific and selective tasks under the control of an external stimulus that switches “ON” and “OFF” their electronic properties. While the interest in single-ion magnets (SIMs) lies in their potential applications in information storage and quantum computing, the switching of their slow magnetic relaxation associated with host–guest processes is insufficiently explored. Herein, we report a unique example of a mononuclear cobalt(II) complex in which geometrical constraints are the cause of easy and reversible water coordination and its release. As a result, a reversible and selective colour and SIM behaviour switch occurs between a “slow-relaxing” deep red anhydrous material (compound 1) and its “fast-relaxing” orange hydrated form (compound 2). The combination of this optical and magnetic switching in this new class of vapochromic and thermochromic SIMs offers fascinating possibilities for designing multifunctional molecular materials.