Double‐Decker Paramagnetic {(K)(H3Hhp)2}⋅2− Radical Dianions Comprising Two [30]Trithia‐2,3,5,10,12,13,15,20,22,23,25,30‐Dodecaazahexaphyrins and a Potassium Ion

Reduction of free‐base [30]trithia‐2,3,5,10,12,13,15,20,22,23,25,30‐dodecaazahexaphyrin (H₃Hhp) yields {cryptand[2.2.2](K)}₂{(K)(H₃Hhp)₂}?4C₆H₄Cl₂ ( 1 ) containing double‐decker {(K)(H₃Hhp)₂} ^{? 2?} radical dianions, whose structure was elucidated using X‐ray diffraction. Potassium ion forms 12 short (K⁺)???N(H₃Hhp) contacts with two H₃Hhp macrocycles in the 3.048–3.157 Å range. Dianions have S=1/2 spin state manifesting an effective magnetic moment of 1.64 μ_B at 300 K and a narrow Lorentzian electron paramagnetic resonance signal. Quantum chemical calculations support the ionic nature of the (K⁺)‐N(H₃Hhp) interactions and the nearly equal distribution of the ?1.5 charge over each macrocycle. H₃Hhp takes the role of an aza‐crown ether in free‐base reduced state and forms a new type of double‐decker complex.