Syntheses, structures and magnetic properties of three new ion-pair complexes containing transition metal bis(malconitriledithiolate) anion and radical cations

Three new ion-pair complexes (m-MPYNN)2Ni(mnt)2 (1), (p-MPYNN)2Ni(mnt)2 (2) and (p-MPYNN)2Cu(mnt)2 (3) (m- or p-MPYNNI = [3- or4- (4,4,5,5-tetramethyl-1-oxido-3-oxyl-4,5-dihydro-3H-imidazol-2′-yl)-1-methylpyridinium] iodide, mnt = maleonitriledithiolate) have been prepared and characterized by elemental analyses, IR, single crystal X-ray diffraction and magnetic susceptibility. In complex 1, the m-MPYNN cations form a centrosymmetric dimer, and the [Ni(mnt)2]2− anion lies on a center of inversion. Complexes 2 and 3 show layered packing, and the p-MPYNN cations lie between the layers of the anions. Magnetic susceptibility measurements in the temperature range 2–300 K show that the three complexes exhibit weak antiferromagnetic behaviors. The behavior of complex 1 was explained with the singlet-triplet model.

Graphical abstractThree ion-pair complexes with M(mnt)22- (M = Cu, Ni) cations and m- or p-MPYNN cations have been synthesized and characterized. The m-MPYNN cations in complex 1 show a centrosymmetric dimer. Magnetic investigations reveal that they all have weak antiferromagnetic interactions.Figure optionsDownload full-size imageDownload as PowerPoint slide