Preparation of double decker {Li3(Cl−)(Hhp)}22− dianions and H2TPCor− monoanions by deprotonation of free-base trithiododecaazahexaphyrin (H3Hhp) and triphenylcorrole (H3TPCor) macrocycles

Nazarov, Dmitry I.; Khasanov, Salavat S.; Rompanen, Ivan A.; Ivanov, Evgenii N.; Койфман, О. И.; Islyaikin, M. K.; Konarev, Dmitri V.

doi:10.1016/j.poly.2021.115198

Cited by 4 publications

(5 citation statements)

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“…The C–N bonds of types 1 and 2 exhibit a strong alternation in pristine substituted H 3 Hhp(OC 5 H 11 ) 6 (Scheme ) because the difference between the average lengths of these bonds is 0.082 Å (Table ). This difference decreases to 0.049–0.060 Å at the formation of a lithium derivative with the Hhp 3– macrocycle or the formation of negatively charged H 3 Hhp macrocycles in {(K)(H 3 Hhp) 2 } •2– (the average charge is −1.5 per H 3 Hhp macrocycle) . The insertion of a M 3 O cluster into the Hhp macrocycle and the appearance of an essential negative charge on Hhp redistribute the bond lengths because shorter type 1 C–N bonds are elongated and the longer type 2 C–N bonds are shortened.…”

Section: Resultsmentioning

confidence: 81%

“…Lithium hemihexaphyrazine (Li 3 Hhp) also exists in a crystalline form, allowing the study of its molecular structure and properties. The Li 3 Hhp-coordinated chloride anion forms short contacts with three lithium atoms, forming anionic double-decker {Li 3 Cl(Hhp)} 2 2– dianions . Hemihexaphyrazine complexes of transition metals such as Cu II , Ni II , and Mn II are also known (Scheme ).…”

Section: Introductionmentioning

confidence: 99%

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Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear M^II₃O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions

et al. 2021

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Metal complexes of trithiadodecaazahexaphyrin (Hhp) that contain M II 3 O clusters inside a π-extended trianionic (Hhp 3− ) macrocycle have been prepared. Studies of the magnetic properties of Ni II 3 O(Hhp) and Cu II 3 O(Hhp) reveal a diamagnetic and EPR-silent trianionic (Hhp 3− ) macrocycle and diamagnetic Ni II 3 (O 2− ) or paramagnetic Cu II 3 (O 2− ) tetracations. The positive charge of M II 3 O(Hhp) is compensated by one acetate anion {M II 3 O(Hhp)} + (CH 3 CO 2 − ). The three-electron reduction of {M II 3 O(Hhp)} + yields {cryptand 2) crystalline salts. The magnetic properties of 1 reveal the formation of Hhp 5− and the reduction of nickel(II) to the paramagnetic Ni I ion (S = 1/2), which is accompanied by the formation of the {Ni II 2 Ni I O(Hhp 5− )} 2− dianion. As a result, the magnetic moment of 1 is 1.68 μ B in the 20−220 K range, and a broad EPR signal of Ni I was observed. The Hhp 5− macrocycle has a singlet ground state, but the increase in the magnitude of the magnetic moment of 1 above 220 K is attributed to the population of the triplet excited state in Hhp 5− . The {Ni II 2 Ni I O(Hhp 5− )} 2− dianion is transferred from the doublet excited state to the quartet excited state with an energy gap of 1420 ± 50 K. Salt 1 also shows an unusually strong low-energy NIR absorption, which was observed at 1000−2200 nm. In 2, a highly reduced Hhp •6− radical hexaanion (S = 1/2) coexists with a Cu II 3 (O 2− ) cluster (S = 1/2) in the {Cu II 3 O(Hhp •6− )} 2− dianions. The dianions have a triplet ground state with antiferromagnetic exchange between two S = 1/2 spins with J = −6.4 cm −1 . The reduction of Hhp in both salts equalizes the initially alternated C−N bonds, supporting the increase in the Hhp macrocycle electron delocalization.

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Section: Resultsmentioning

confidence: 81%

Section: Introductionmentioning

confidence: 99%

Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear M^II₃O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions

et al. 2021

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“…Было установлено, что молекулы макроцикла в результате самосборки формируют на поверхности Au(III) протяженные мономолекулярные слои, которые способны к ступенчатому, пространственно-контролируемому с помощью зонда депротонированию, что может представлять интерес для последующего изучения Hhp в качестве материала для записи и хранения информации. [47], бparamagnetic radical dianion {(K)(H3Hhp)2} 2- [48] according to X-ray diffraction data Молекулы H3Hhp, будучи зафиксированными на поверхности, способны координировать диспрозий с образованием комплекса нецентросимметричного типа (рис. 4г).…”

Section: собственно макрогетероциклические соединенияunclassified

“…В результате впервые получен необычный двухпалубный комплекс дианионного типа, где в качестве связующего выступает хлорид-анион (рис. 5) [47].…”

Section: собственно макрогетероциклические соединенияunclassified

Achievements in the Field of Chemistry of Macroheterocyclic Compounds at the Department of Technology of Fine Organic Synthesis

2023

Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.

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The material presented in this review is devoted to scientific research carried out at one of the oldest graduating departments of ISUCT - the Department of Fine Organic Synthesis Technology. For citation: Danilova E.A., Galanin N.E., Islyaikin M.K., Maizlish V.E., Berezina G.R., Rumyantseva T.A., Suvorova Yu.V., Znoiko S.A., Kustova T.V. Achievements in the field of chemistry of macroheterocyclic compounds at the department of technology of fine organic synthesis. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 7. P. 111-119. DOI: 10.6060/ivkkt.20236607. 6826j.

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“…Recently it was shown that due to the presence of nine nitrogen atoms in the inner ring, H 3 Hhp can form a double-decker complex with potassium [28]. Metallation of the macrocycle with diethylamid lithium led to another unusual double-decker structure in which two Li 3 Hhp are joined by Cl atom [29].…”

Section: Introductionmentioning

confidence: 99%

Synthesis and Characterization of Bulky Substituted Hemihexaphyrazines Bearing 2,6-Diisopropylphenoxy Groups

Ivanov,

Almeida-Marrero,

Koifman

et al. 2023

Molecules

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New substituted [30]trithiadodecaazahexaphyrines (hemihexaphyrazines) were synthesized by a crossover condensation of 2,5-diamino-1,3,4-thiadiazole with 4-chloro-5-(2,6-diisopropylphenoxy)- or 4,5-bis-(2,6-diisopropylphenoxy)phthalonitriles. The compounds were characterized by 1H-, 13C-NMR, including COSY, HMBC, and HSQC spectroscopy, MALDI TOF spectrometry, elemental analysis, IR and UV-Vis absorbance and fluorescence techniques.

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Preparation of double decker {Li3(Cl−)(Hhp)}22− dianions and H2TPCor− monoanions by deprotonation of free-base trithiododecaazahexaphyrin (H3Hhp) and triphenylcorrole (H3TPCor) macrocycles

Cited by 4 publications

References 38 publications

Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear M^II₃O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions

Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear M^II₃O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions

Achievements in the Field of Chemistry of Macroheterocyclic Compounds at the Department of Technology of Fine Organic Synthesis

Synthesis and Characterization of Bulky Substituted Hemihexaphyrazines Bearing 2,6-Diisopropylphenoxy Groups

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Preparation of double decker {Li3(Cl−)(Hhp)}22− dianions and H2TPCor− monoanions by deprotonation of free-base trithiododecaazahexaphyrin (H3Hhp) and triphenylcorrole (H3TPCor) macrocycles

Cited by 4 publications

References 38 publications

Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear MII3O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions

Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear MII3O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions

Achievements in the Field of Chemistry of Macroheterocyclic Compounds at the Department of Technology of Fine Organic Synthesis

Synthesis and Characterization of Bulky Substituted Hemihexaphyrazines Bearing 2,6-Diisopropylphenoxy Groups

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Product

Resources

About

Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear M^II₃O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions

Dianionic States of Trithiadodecaazahexaphyrin Complexes with Homotrinuclear M^II₃O Clusters (M = Ni and Cu): Crystal Structures, Metal- Or Macrocycle-Centered Reduction, and Doublet–Quartet Transitions in the Dianions