Terephthalamide-containing analogues of TREN-Me-3,2-HOPO.

A series of terephthalamide-containing analogues based on TREN-Me-3,2-HOPO have been prepared. These analogues contain one, two, or three bidentate 2,3-dihydroxyterephthalamide (TAM) units in place of the 3,2-hydroxypyridinone (HOPO) units on the parent hexadentate ligand. One representative ligand in the series, TRENHOPOTAM2, and its gallium complex have been structurally characterized by X-ray diffraction. TRENHOPOTAM2 crystallizes in the monoclinic space group P2(1)/c with cell parameters a = 16.0340(17) A, b = 17.0609(18) A, c = 16.0695(17) A, beta = 113.837(2) degrees, and Z = 4. Ga[TRENHOPOTAM2] also crystallizes in the monoclinic space group P2(1)/c, with cell parameters a = 16.3379(14) A, b = 15.2722(13) A, c = 19.4397(17) A, beta = 91.656(2) degrees, and Z = 4. The conformation of the TRENHOPOTAM2 ligand structure suggests that the ligand is predisposed for metal ion binding. The aqueous protonation and ferric ion coordination chemistry of all ligands in the series were examined using potentiometric and spectrophotometric methods, giving log formation constants of 34.6(2) (beta110) and 38.8(2) (beta111) for the ferric TRENHOPO2TAM complexes, 41.0(3) (beta110) and 45.4(3) (beta111) for the ferric TRENHOPOTAM2 complexes, and 45.2(2) (beta110) and 50.9(2) (beta111) for the ferric TRENTAM3 complexes. These thermodynamic data confirm that adding terephthalamide units to a hydroxypyridinone-containing ligand tends to increase the stability of the resulting iron complex. The ferric TRENTAM3 complex is one of the most stable iron complexes yet reported.