NMR spectroscopic studies reveal that binding of Na+ by tris(2-methoxyphenyl)amine (3) brings two of these tripod ethers together about the metal ion; the related double-tripod-ether ionophore 1,2-bis[2-(bis(2-methoxyphenyl)amino)phenoxy]ethane (4), in which two triarylamines are covalently attached, binds LiI, LiBPh(4), NaI, NaBPh(4), and KB(4-ClPh)(4). Dynamic NMR puts lower limits on binding free energies of 4 for Na+ (71.8 kJ mol(-1)) and K+ (66.8 kJ mol(-1)) ions. X-ray studies of 3(2) . NaBPh(4), 4 . NaBPh(4), 4 . NaB(4-ClPh)(4), and 4 . KB(4-ClPh)(4) . CH3NO2 show eight-coordinate M(+) ions bound between crystallographically independent, homochiral triarylamine tripod ethers in structures reminiscent of alkali metal [2.2.2] cryptates. Complexes crystallize as follows : 3(2) . NaBPH4, monoclinic, P2(1)/c, Z = 4, a = 10.701(3) Angstrom, b = 37.593(3) Angstrom, c = 13.774(2) Angstrom, and beta = 98.24(2)degrees; 4 . NaBPh(4), triclinic, P (1) over bar, Z = 2, a = 12.157(1) Angstrom, b = 14.811(1) Angstrom, c = 15.860(2) Angstrom, alpha = 105.400(8)degrees, beta = 91.594(9)degrees, and gamma = 95.354(8)degrees : 4 . NaB(4-ClPh)(4), monoclinic, P2(1)/n, Z = 4, a = 13.652(5) Angstrom, b = 18.75(1) Angstrom, c = 22.805(5) Angstrom, and beta = 92.21(5)degrees; 4 . KB(4-ClPh)(4) . CH3NO2, monoclinic, Pn, Z = 2, a = 13.663(4) Angstrom, b = 12.228(3) Angstrom, c = 18.712(8) Angstrom, and beta = 91.45(3)degrees. They show variable N-M-N angles; 3(2) . NaBPh(4) is surprisingly bent (angle N-Na-N = 154.5 degrees), while the 4 . M(+) complexes are normal : nearly linear for Na+ (angle N-Na-N = 178.6, 178.1 degrees) and again bent with the larger K+ (angle N-K-N = 164.5 degrees). Finally, free 4 is structurally similar to 3; it crystallizes in the triclinic space group P (1) over bar, with Z = 2, a = 8.068(1) Angstrom, b = 14.599(2) Angstrom, c = 16.475(3) Angstrom,alpha = 115.43(1)degrees, beta = 92.51(1)degrees, and gamma = 90.40(1)degrees.