A Novel Hemiporphyrazine Comprising Three Isoindolediimine and Three Thiadiazole Units

Abstract

Incorporation of three metal ions (Ni or Cu) in the macrocyclic ring and the formation of hexamers following a 3+3 approach are novel features of the hemiporphyrazines (one example shown) formed by the condensation of 2,5‐diamino‐1,3,4‐triazole with isoindolediimines. This is in contrast to the corresponding reactions with diaminotriazoles, which afford 2+2 products.

Synthesis and Properties of Hexa(4-tert-butylphenoxy) Substituted [30]Trithiadodecaazahexaphyrin and its Metal Complexes

“…[1,2] These compounds possess a variety of unprecedented properties such as nonaromatic character despite formally fitting the Hückel's rule, [3,4] tautomeric behavior, [5,6] high thermal stability, [7] and ability to accommodate up to three transition metals such as Ni…”

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

“…[10,11] Herein, a nonsubstituted H 3 Hhp was obtained by condensation of phthalonitrile and 2,5-diamino-1,3,4-thiadiazole in phenol. [23] To avoid the use of this highly toxic solvent, we have established a new synthetic protocol, employing ethylene glycol as a reaction medium (Scheme 1).…”

“…[1][2][3][4][5][6] A principal aspect derived from structures of these compounds is aromaticity of central core and applicability of Hückel's rule to describe its electronic structure. [7][8][9] Among expanded compounds, Mc's of ABABAB-type (hemihexaphyrazine, H 3 Hhp) containing six consecutively interlinked 1,3,4-thiadiazole (A) and isoindole (B) subunits bridged by nitrogen atoms [10,11] induce a particular interest. Indeed, various substituted macroheterocyclic compounds of this type were synthesized to date [12][13][14][15][16][17][18] and their structures were confirmed by gas electron diffraction (GED) [19,20] and single crystal X-ray diffraction [21] methods.…”

“…This extended macrocyclic system is able to bind up to three transition metal atoms. [10,11,22] Since nonsubstituted H 3 Hhp is only slightly soluble in organic solvents, [23] information on the metal complexes of these compounds was limited by synthesis of metal complexes of substituted hemihexaphyrazines. Therefore, the aim of this work is the synthesis of transition metal complexes based on the unsubstituted H 3 Hhp.…”

Synthetic approaches to asymmetric phthalocyanines and their analogues

“…[64][65][66][67][68][69] In order to satisfy this demand, over the last few decades numerous research groups have made great strides in the preparation of asymmetric phthalocyanines and their analogues including triazole-, thiadiazole-, and hemiporphyrazines. [64][65][66][67][68][69][70][71][72][73][74] The chemistry of asymmetric phthalocyanines had a slow start. The first report on an asymmetric phthalocyanine analogue by Linstead and co-workers dates back to 1955, 75 followed by work of Luk'yanets and co-workers in 1979.…”