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As materials science is moving towards the synthesis, the study and the processing of new materials exhibiting well-defined and complex functions, the synthesis of new multifunctional materials is one of the important challenges. One of these complex physical properties is magneto-chiral dichroism which arises, at second order, from the coexistence of spatial asymmetry and magnetization in a material. Herein we report the first measurement of strong magneto-chiral dichroism in an enantiopure chiral ferromagnet. The ab initio synthesis of the enantiopure chiral ferromagnet is based on an enantioselective self-assembly, where a resolved chiral quaternary ammonium cation imposes the absolute configurations of the metal centres within chromium-manganese two-dimensional oxalate layers. The ferromagnetic interaction between Cr(III) and Mn(II) ions leads to a Curie temperature of 7 K. The magneto-chiral dichroic effect is enhanced by a factor of 17 when entering into the ferromagnetic phase.

In this critical review, it is shown how the introduction of chirality and the control of the absolute configurations of chiral elements in molecular magnets allow obtaining enantiopure chiral magnets (ECM), an archetype of multifunctional materials. This task has been recognised as a major challenge for both chemists and physicists of molecular magnetism. To reach this goal, the former have combined the rational approaches towards molecular-based magnets and of enantiopure metal-organic frameworks. They have used enantiopure stable radicals, ligands from the chiral pool, enantiopure coligands associated with achiral connectors or enantioselective self-assembly to successfully reach their synthetic targets. They were motivated by the will to obtain suitable systems for the experimental demonstration of the influence of enantiomeric purity on the physico-chemical properties. This influence can be found in the magnetic properties themselves but, most interestingly, in the coexistence and interaction between the properties arising from controlled non-centrosymmetry. Thus the combination of natural circular dichroism, second harmonic generation or ferroelectricity with long-range magnetic ordering can give birth to new properties like magneto-chiral dichroism, magnetisation induced second harmonic generation or multiferroicity. The two former synergetic effects have already been demonstrated in enantiopure chiral magnets. The third one remains a challenging target that can be reached by adapting strategies developed towards enantiopure molecular ferroelectrics (119 references).

A complex-as-ligand strategy to get a multifunctional molecular material led to a metal-organic framework with the formula (NH(4))(4)[MnCr(2)(ox)(6)]·4H(2)O. Single-crystal X-ray diffraction revealed that the anionic bimetallic coordination network adopts a chiral three-dimensional quartz-like architecture. It hosts ammonium cations and water molecules in functionalized channels. In addition to ferromagnetic ordering below T(C) = 3.0 K related to the host network, the material exhibits a very high proton conductivity of 1.1 × 10(-3) S cm(-1) at room temperature due to the guest molecules.

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The absence of centrosymmetry in the enantiopure chiral magnet [N(CH(3))(n-C(3)H(7))(2)(C*H(CH(3))C(2)H(5))][Mn(II)Cr(III)(ox)(3)] allows the observation of bulk second harmonic generation (SHG) in this material. At low temperature, the onset of magnetization gives birth to a magnetization-induced SHG (MSHG) contribution. With an angular shift of 13.1 degrees upon magnetization reversal, the MSHG effects appear to be much larger than the corresponding linear magneto-optical effects. Thanks to the single-crystalline state of the sample, the variation of the signal with the orientation of the magnetic field and/or the angle between the polarization of the incident radiation and the outgoing SHG signal in the paramagnetic and ferromagnetic phases is reproduced and well-understood through the use of a symmetry-based analysis of the nonlinear susceptibility tensor.

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