Inoue Michiko B., Velazquez Enrique F., Medrano Felipe, Ochoa Karen L., Galvez J. C., Inoue Motomichi, Fernando Quintus
Department of Chemistry, University of Arizona, Tucson, Arizona 85721-0041, and CIPM, Universidad de Sonora, Apartado Postal 130, Hermosillo, Sonora 83000, Mexico.
Inorg Chem. 1998 Aug 10;37(16):4070-4075. doi: 10.1021/ic980238c.
A chelating cyclophane has been synthesized by cyclocondensation of two ethylenediaminetetraacetic (EDTA) units with two p-phenylenediamine units: the resulting cyclophane is 2,9,18,25-tetraoxo-4,7,20,23-tetrakis(carboxymethyl)-1,4,7,10,17,20,23,26-octaaza[10.10]paracyclophane, abbreviated as (bis-edtapdn)H(4). Cyclocondensation of two EDTA and two 1,5-diaminonaphthalene units has given the naphthalenophane, 2,9,22,29-tetraoxo-4,7,24,27-tetrakis(carboxymethyl)-1,4,7,10,21,24,27,30-octaaza10.10naphthalenophane, (bis-edtanap)H(4). Studies of electronic and EPR spectra have been carried out on the binuclear Cu(2+) complexes of these new ligands and of related chelating cyclophanes, 2,9,25,32-tetraoxo-4,7,27,30-tetrakis(carboxymethyl)-1,4,7,10,24,27,30,33-octaaza[10.1.10.1]paracyclophane, abbreviated as (bis-edtabpm)H(4), and 2,9,25,32-tetraoxo-4,7,27,30-tetrakis(carboxymethyl)-1,4,7,10,24,27,30,33-octaaza-17,40-dioxa[10.1.10.1]paracyclophane, abbreviated as (bis-edtabpe)H(4). Common features of these chelating cyclophanes are as follows: (1) amino, amide, and pendant carboxymethyl donor groups are substituents in the cyclophane ring, and (2) the amide groups are directly bound to the aromatic groups. These ligands formed neutral binuclear Cu(2+) chelates Cu(2)L that are water-insoluble. In alkaline solutions, these Cu(2+) complexes were converted to anionic chelates Cu(2)(LH(-)(4))(-) in which deprotonated amide nitrogens coordinated Cu(2+) ions. These anionic metal chelates of (bis-edtapdn)H(4), (bis-edtabpm)H(4), and (bis-edtabpe)H(4) exhibited three pi-pi transition bands in the spectral range 240-340 nm, in contrast to the uncoordinated cyclophanes, which showed a single band in this spectral range. The unusual pi-pi transition spectra of the Cu(2)(LH(-)(4))(-) complexes originate from the combined effect of metal-ligand charge transfer and proximity of the pi systems. The absorption and emission spectra of (bis-edtanap)H(4) were also influenced by coordination with copper. The EPR spectrum of Cu(2)(bis-edtanapH(-)(4))(-) in a methanol glass matrix showed a hyperfine structure due to the spin exchange between two Cu(2+) ions. These unusual spectral and magnetic properties arise from the strong coordination between Cu(2+) ions and deprotonated amide nitrogens that are bound to the pi systems.
通过乙二胺四乙酸（EDTA）的两个单元与对苯二胺的两个单元进行环缩合反应合成了一种螯合环芳：所得环芳为2,9,18,25 - 四氧代 - 4,7,20,23 - 四（羧甲基）- 1,4,7,10,17,20,23,26 - 八氮杂[10.10]对环芳，简称为(bis - edtapdn)H(4)。两个EDTA单元与两个1,5 - 二氨基萘单元的环缩合反应得到萘并环芳，即2,9,22,29 - 四氧代 - 4,
