Metal Complexation of Calix[4]azacrown Derivatives – Evidence for Communication Between Upper and Lower Functionalised Rims

Abstract

The coordination chemistry of calix[4]azacrowns obtained from the reaction of a diester calix[4]arene with diethylenetriamine provided unusual copper(II) and manganese(II) complexes in which calix[4]azacrown acts as a bidentate N,O‐donor ligand, in some cases, but as a unidentate N‐donor ligand, in other cases. The first example of a binuclear ruthenium(II)/manganese(II) complex, involving the calix[4]arene framework as the bridging ligand, is also reported. The calix[4]arene framework consists of a bipyridyl unit connected at the upper rim of the calix[4]arene, through an amide linkage, and an azacrown unit at the lower rim, also connected through amide groups. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

Coordination chemistry of calix[4]arene derivatives with lower rim functionalisation and their applications

“…They were able to assign a band at 450 nm in the absorption spectrum of a AuTMPyP/ZnTMPyP/AuTMPyP/(C 4 TsTc) 4 species as arising from a Zn(II) → Au(III) energy transfer process. McGinley and co-workers have synthesised calix [4]arene derivatives which are capable of complexing different transition metal ions at both the upper and lower rims of the calix [4]arene [169]. They have synthesised mixed metal complexes with ruthenium(II) on the upper rim and several transition metal ions, including copper(II) and manganese(II) on the lower rim.…”

Self-assembly of calix[4]arene amine derivatives

“…The samples were then heated to 273 K and allowed to cool to allow electron transfer to occur and this revealed that there was a . This data suggests that the two metals are in communication with each other despite the fact that they are not directly linked through a conjugated system to one another 107 .…”

Novel lariat calix[4]-1,3-aza-crowns with two branched chains — The excellent phase transfer catalysts for nucleophilic substitution reaction

“…[8][9][10][11][12][13][14][15][16][17] In the field of crown ethers, it is well-known that the lariat crown ethers with branched chains usually show outstanding complexation abilities for guest due to the coordinated recognition of crown ether chains and branched chains. However, in the field of calixcrowns, although many calixcrowns were reported, only Bitter and co-workers 18,19 and Bond et al 20 reported several lariat calix [4]-aza-crowns with one amino-branched chain. These lariat calix [4]-azacrowns exhibited excellent recognition properties due to the favorable synergistic complexation [18][19] but they were not concerned with their phase catalytic properties.…”