Double‐Decker Paramagnetic {(K)(H 3 Hhp) 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 (H 3 Hhp) yields {cryptand[2.2.2](K)} 2 {(K)(H 3 Hhp) 2 }⋅4C 6 H 4 Cl 2 ( 1 ) containing double‐decker {(K)(H 3 Hhp) 2 } ⋅ 2− radical dianions, whose structure was elucidated using X‐ray diffraction. Potassium ion forms 12 short (K + )⋅⋅⋅N(H 3 Hhp) contacts with two H 3 Hhp 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(H 3 Hhp) interactions and the nearly equal distribution of the −1.5 charge over each macrocycle. H 3 Hhp takes the role of an aza‐crown ether in free‐base reduced state and forms a new type of double‐decker complex.