With adequate building blocks, metal–organic frameworks (MOFs) can combine magnetic ordering and porosity. This makes MOFs a promising platform for the development of stimuli-responsive materials that show drastically different magnetic properties depending on the presence or absence of guest molecules within their pores. Here we report a CO₂-responsive magnetic MOF that converts from ferrimagnetic to paramagnetic on CO₂ adsorption, and returns to the ferrimagnetic state on CO₂ desorption. The ferrimagnetic material is a layered MOF with a [D⁺–A⁻–D] formula, produced from the reaction of trifluorobenzoate-bridged paddlewheel-type diruthenium(ii) clusters as the electron donor (D) with diethoxytetracyanoquinodimethane as the electron acceptor (A). On CO₂ uptake, it undergoes an in-plane electron transfer and a structural transition to adopt a [D–A–D] paramagnetic form. This magnetic phase change, and the accompanying modifications to the electronic conductivity and permittivity of the MOF, are electronically stabilized by the guest CO₂ molecules accommodated in the framework.

如果有足够的构造块，金属有机框架（MOF）可以将磁有序性和孔隙率结合在一起。这使MOF成为开发刺激反应性材料的有前途的平台，这些材料会根据其孔中是否存在客体分子而表现出截然不同的磁性。在这里，我们报告了一个CO ₂响应磁性MOF，该MOF在吸附CO _2时从亚铁磁转变为顺磁，并在CO ₂解吸时返回到亚铁磁状态。亚铁磁性材料是具有[D ⁺ –A ⁻ –D]分子式的层状MOF ，由三氟苯甲酸酯桥连的桨轮型二钌（ii）以二乙氧基四氰基喹二甲烷为电子受体（A）聚集为电子供体（D）。在吸收CO _2时，它经历面内电子转移和结构转变，以采用[D–A–D]顺磁性形式。通过容纳在框架中的客体CO ₂分子，该磁性相变以及对MOF的电子电导率和介电常数的随之而来的修饰被电子稳定。