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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
Author(s) -
Konarev Dmitri V.,
Khasanov Salavat S.,
Islyaikin Mikhail K.,
Otsuka Akihiro,
Yamochi Hideki,
Kitagawa Hiroshi,
Lyubovskaya Rimma N.,
Ivanov Evgenii N.,
Koifman Oskar I.,
Zhabanov Yuriy A.
Publication year - 2020
Publication title -
chemistry – an asian journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.18
H-Index - 106
eISSN - 1861-471X
pISSN - 1861-4728
DOI - 10.1002/asia.201901518
Subject(s) - chemistry , cryptand , electron paramagnetic resonance , paramagnetism , crystallography , ionic bonding , ion , radical ion , nuclear magnetic resonance , physics , organic chemistry , quantum mechanics
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.