Tunable Reduction of 2,4,6‐Tri(4‐pyridyl)‐1,3,5‐Triazine: From Radical Anion to Diradical Dianion to Radical Metal–Organic Framework

The reduction of 2,4,6‐tri(4‐pyridyl)‐1,3,5‐triazine (TPT) with alkali metals resulted in four radical anion salts (1, 2, 4 and 5) and one diradical dianion salt (3). Single‐crystal X‐ray diffraction and electron paramagnetic resonance (EPR) spectroscopy reveal that 1 contains the monoradical anion TPT.− stacked in one‐dimensional (1D) with K+(18c6) and 2 can be viewed as a 1D magnetic chain of TPT.−, while 4 and 5 form radical metal‐organic frameworks (RMOFs). 1D pore passages, with a diameter of 6.0 Å, containing solvent molecules were observed in 5. Variable‐temperature EPR measurements show that 3 has an open‐shell singlet ground state that can be excited to a triplet state, consistent with theoretical calculation. The work suggests that the direct reduction approach could lead to the formation of RMOFs. Within the framework: By controlling of the reductants and reaction conditions, reduction of 2,4,6‐tri(4‐pyridyl)‐1,3,5‐triazine (TPT) resulted in four radical anion salts and a diradical dianion salt. One of the radical anion salts forms one‐dimensional (1D) magnetic chain of TPT.−, and two of the others form radical metal‐organic frameworks (RMOFs). TPT..2− in the diradical dianion salt features an open‐shell singlet ground state.