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 (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 angstrom range. Dianions have S=1/2 spin state manifesting an effective magnetic moment of 1.64 mu(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.