Tuning Magnetic Interactions Between Triphenylene Radicals by Variation of Crystal Packing in Structures with Alkali Metal Counterions

The monoanion of triphenylene (C₁₈H₁₂, 1) was generated in THF using several alkali metals (Na, K, Rb, and Cs) as reducing agents and crystallized with the corresponding cations in the presence of 18-crown-6 ether. The UV-vis spectroscopy points to the metal-dependent coordination environment of the triphenylene monoanion-radicals, 1^·-, in solution. The X-ray diffraction characterization confirmed the formation of a solvent-separated ion pair (SSIP) with sodium ions, [{Na⁺(18-crown-6)(THF)₂}(1^·-)] (2), and three contact-ion pair (CIP) complexes formed by larger alkali metal ions, [{K⁺(18-crown-6)}(1^·-)] (3), [{Rb⁺(18-crown-6)}(1^·-)] (4), and [{Cs⁺(18-crown-6)}(1^·-)] (5). Structural analysis of the series reveals a notable geometry perturbation of the triphenylene framework in 2 caused by one-electron acquisition, which is further enhanced by direct metal binding in 3-5. This has been correlated with the aromaticity changes and charge redistribution upon one-electron reduction of 1, as revealed by the computational studies. The EPR spectroscopy and magnetic susceptibility measurements confirm antiferromagnetic interactions corresponding to an S = 1/2 system in the solid state. The magnetic behavior of 3-5 correlates with the arrangement of triphenylene radicals in the crystal structures. All three compounds exhibit antiferromagnetic (AFM) interactions between S = 1/2 radicals in the solid state, but the exchange coupling in 4 and 5 is notably stronger than that in 3, which leads to AFM ordering at 3.8 K in 4 and at 2.0 K in 5. The magnetic phase transitions in 4 and 5 can be interpreted as originating from interactions between the chains of the AFM-coupled S = 1/2 radicals.