Homotrinuclear Сomplexes of [30]Trithiadodecaazahexaphyrine with Transition Metals: Ni(II), Cu(II) and Mn(II)

Abstract

Homotrinuclear complexes were synthesized by reaction of [30]trithiadodecaazahexaphyrine (hemihexaphyrazine) with nickel(II), copper(II) or manganese(II

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

“…Because KC 8 is used in excess, each H 3 Hhp can extract even larger amounts of potassium ions (e.g., forming a 1:1 complex with potassium), but such a phase was not found in the solid state. Thus, H 3 Hhp is a rare example of a macrocycle that can bind up to three metal atoms in the vacancies formed by three nitrogen atoms, including nitrogen of isoindole units inside the macrocycle . It can also be an aza‐crown ether that binds metals by six nitrogen atoms of three thiadiazole groups, forming a double‐decker complex (hydrogen at nitrogen atoms of the isoindole units preserved at such coordination).…”

“…Thus, H 3 Hhp is ar are example of am acrocycle that can bind up to three metal atoms in the vacancies formed by three nitrogen atoms, including nitrogen of isoindole units inside the macrocycle. [17] It can also be an aza-crown ether that binds metals by six nitrogen atoms of three thiadiazole groups,f orming ad ouble-decker complex (hydrogen at nitrogena toms of the isoindole units preserved at such coordination). The coordination of the potassium ion is of interest because generally double-deckerc omplexes of the porphyrina nd phthalocyanine macrocyclesa re formedm ainly with high-valent metals of al arge size, such as lanthanides, Hf IV ,S n IV ,I n III ,and some other metals.…”

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

“…Hemihexaphyrazine complexes of transition metals such as Cu II , Ni II , and Mn II are also known (Scheme ). They can be obtained by boiling H 3 Hhp in phenol with an excess of metal­(II) acetates. The mass spectra of these complexes reveal the presence of M 3 O units, which according to the calculations are positioned in the center of a planar macrocycle.…”

“…The mass spectra of these complexes reveal the presence of M 3 O units, which according to the calculations are positioned in the center of a planar macrocycle. Oxygen atoms for the formation of M 3 O are most likely extracted from phenol (the solvent for the syntheses of these complexes), the atmosphere, or water, which is used to wash these compounds during preparation . The crystal structures and magnetic properties of these complexes are still unknown.…”

Hemihexaphyrazine and Thiadiazole Annulated Hemihexaphyrazine: A Theoretical Insight into Aromaticity and Energetics of Hydrogen Bonding

“…Investigations of the molecular structure and tautomeric preference of macroheterocyclic systems have been the subject of the many recent studies. [1][2][3][4][5][6][7] Among a huge number of macrocycles, hemihexaphyrazins of ABABABtype attract a great interest due to their unusually high symmetrical structures, [4][5][6] expanded coordination cavity with enormous potential in coordination chemistry [8][9][10][11] and catalysis, [12] and molecular level information storage. [6] In our recent work [13] a study of tautomeric preference and intramolecular hydrogen bonding was performed for the thiadiazole annulated hemihexaphyrazine (TDAHHp, Scheme 1).…”