Thiadiazole-Derived Expanded Heteroazaporphyrinoids

Abstract

Heteroannulenes 1 and 3 containing three subunits of isoindole or pyrrole, respectively, three 1,3,4-thiadiazole moieties, and six aza-bridges have been synthesized by reaction of the corresponding diiminoisoindoline or diiminopyrroline with 2,5-diamino-1,3,4-thiadiazole. These conjugated nonaromatic 30 π-electron macrocycles coordinate three metal ions within their central cavity and constitute one of the rare examples of expanded heteroazaporphyrinoids.

Synthesis and Properties of AABAAB-Type Macroheterocyclic Compounds with Fragments of 1,2,4- and 1,3,4-Thiadiazole

“…[9,10] Their structures were confirmed by gas electron diffraction and X-ray crystallographic analysis. [11][12][13][14] The compounds exhibit an expanded cavity which is able to contain up to three transition metal atoms, [8,15,16] possess high thermal stability, [17] show interesting electrochemical and photophysical properties [14,18] and are of particular interest as objects of supramolecular chemistry.…”

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

“…[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.…”