Obtaining room-temperature (RT) molecule-based magnets is a long-sought-after goal in the materials community. However, so far, most of the reported magnets based on charge-transfer salts, pure organic radicals, and coordination polymers have shown low magnetic ordering temperatures. Herein, we propose an alternative approach for magnets by using covalently linked organic radical frameworks, in which neighboring radicals are ferromagnetically coupled. Stable hexacyanotrimethylenecyclopropanide radical anions ([CN6CP]M, M = K⁺ [1a], n-Bu₄N⁺ [1b]) were found to undergo either thermal polymerization in the solid state at a relatively low temperature (300°C) without the need for ZnCl₂ (for 1a) or trifluoromethanesulfonic-acid-mediated polymerization at 60°C (for 1b) to give 1,3,5-triazine-linked porous organic radical framework 2 or 3, respectively. The resulting material 2 exhibited spontaneous magnetization at RT with typical hysteresis of ferromagnets, and the ordering temperature was estimated to be 465 K, whereas the magnetic behavior of 3 is more like superparamagnetism.

在材料界，获得基于室温（RT）分子的磁体是一个长期追求的目标。但是，到目前为止，大多数报道的基于电荷转移盐，纯有机自由基和配位聚合物的磁体都显示出较低的磁序温度。在这里，我们提出了一种使用共价连接的有机自由基骨架的磁体替代方法，其中相邻的自由基是铁磁耦合的。发现稳定的六氰基三亚甲基环丙烷阴离子自由基（[CN6CP] M，M = K ⁺ [ 1a ]，n -Bu ₄ N ⁺ [ 1b ]）在较低的温度（300℃）下以固态进行热聚合，而没有对ZnCl的需求₂（对于1a）或三氟甲磺酸介导的聚合反应在60°C（对于1b），分别得到1,3,5-三嗪连接的多孔有机自由基骨架2或3。所得到的材料2在室温下呈现出自发磁化，并具有典型的铁磁体磁滞，其有序温度估计为465 K，而3的磁行为更像是超顺磁性。