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Magnetic photoswitching is a highly important but relatively rare phenomenon for enabling optical writing/reading of the magnetic state of a molecule. In this work, an unprecedented site-selective double photoswitching is reported from the assembly of two different "photomagnetic chromophores" into a single hexanuclear molecule: namely, a spin-crossover Fe(II) center exhibiting light-induced excited spin state trapping (LIESST) and a photochemically active octacyanometalate(IV) unit. Four different magnetization levels are accessible through the appropriate combination of violet/red light and temperature, results that highlight the potential of photomagnetic molecules as future molecular memory cells.

"Converting" light energy to magnetization is the attribute of molecule-based compounds called photomagnets and is inaccessible for conventional magnetic solids. The design and synthesis of such compounds, however, is a formidable challenge, and only a few examples are known, all with rather low magnetic ordering temperatures well below the boiling point of liquid nitrogen. Herein, a cyanide-bridged coordination polymer, {[Mn II (imidazole)] 2 [W IV (CN) 8 ]} n , exhibiting the highest light-induced magnetic ordering temperature ever observed and a magnetic hysteresis loop up to 90 K is reported. The photomagnetic effect results from the blue light excitation (450 nm) of the constituent octacyanotungstate(IV) moiety, which then couples magnetically with manganese(II), resulting in light-induced ferrimagnetic ordering. The reported coordination framework shows also outstanding water sorption properties that are strongly correlated with the photomagnetic functionality. The photoswitching observed in the anhydrous state is completely quenched by the reversible capture of water, with the fully hydrated phase becoming practically non-photomagnetic.

The syntheses, structures, and magnetic properties of four new complex salts, (PPN){[Mn(III)(salphen)(MeOH)]2[M(III)(CN)6]}·7MeOH (Mn2M·7MeOH) (M = Fe, Ru, Os and Co; PPN(+) = bis(triphenylphosphoranylidene)ammonium cation; H2salphen = N,N'-bis(salicylidene)-1,2-diaminobenzene), and a mixed metal Co/Os analogue (PPN){[Mn(III)(salphen)(MeOH)]2[Co(III)0.92Os(III)0.08(CN)6]}·7MeOH were undertaken. It was found that all compounds exhibit switchable single-molecule magnet (SMM) and exchange-bias behavior depending on the interstitial methanol content. The pristine (PPN){[Mn(salphen)(MeOH)]2[Os(CN)6]}·7MeOH (Mn2Os·7MeOH) behaves as an SMM with an effective barrier for the magnetization reversal, (Ueff/kB), of 17.1 K. Upon desolvation, Mn2Os exhibits an increase of Ueff/kB to 42.0 K and an opening of the hysteresis loop observable at 1.8 K. Mn2Os·7MeOH shows also exchange-bias behavior with magnetic hysteresis loops exhibiting a shift in the quantum tunneling to 0.25 T from zero-field. The Fe(III) and Ru(III) analogues were prepared as reference compounds for assessing the effect of the 5d versus 4d and 3d metal ions on the SMM properties. These compounds are also SMMs and exhibit similar effects but with lower energy barriers. These findings underscore the importance of introducing heavy transition elements into SMMs to improve their slow relaxation of the magnetization properties. The (PPN){[Mn(III)(salphen)(MeOH)]2[Co(III)(CN)6]}·7MeOH (Mn2Co·7MeOH) analogue with a diamagnetic Co(III) central atom and the mixed Co/Os (PPN){[Mn(III)(salphen)(MeOH)]2[Co(III)0.92Os(III)0.08(CN)6]}·7MeOH (Mn2Co/Os·7MeOH) "magnetically diluted" system with a 9:1 Co/Os metal ratio were prepared in order to further probe the nature of the energy barrier increase upon desolvation of Mn2Os. In addition, inelastic neutron scattering and frequency-domain Fourier-transform THz electron paramagnetic resonance spectra obtained on Mn2Os·7MeOH and Mn2Os in combination with the magnetic data revealed the presence of anisotropic exchange interactions between Mn(III) and Os(III) ions.

Photomagnetic compounds are usually achieved by assembling preorganized individual molecules into rationally designed molecular architectures via the bottom-up approach. Here we show that a magnetic response to light can also be enforced in a nonphotomagnetic compound by applying mechanical stress. The nonphotomagnetic cyano-bridged Fe(II)-Nb(IV) coordination polymer {[Fe(II)(pyrazole)4]2[Nb(IV)(CN)8]·4H2O}n (FeNb) has been subjected to high-pressure structural, magnetic and photomagnetic studies at low temperature, which revealed a wide spectrum of pressure-related functionalities including the light-induced magnetization. The multifunctionality of FeNb is compared with a simple structural and magnetic pressure response of its analog {[Mn(II)(pyrazole)4]2[Nb(IV)(CN)8]·4H2O}n (MnNb). The FeNb coordination polymer is the first pressure-induced spin-crossover photomagnet.

The pentanuclear compound [V(II)(tmphen)2]3[Mo(III)(CN)6]2 (tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline) exhibits a record antiferromagnetic exchange coupling constant of J(V-Mo) = -114 cm(-1). This is the first example of a heterobimetallic cyanide compound with such strong magnetic coupling.