TY - JOUR
T1 - Metal sulfonatocalix[4,5]arene complexes
T2 - Bi-layers, capsules, spheres, tubular arrays and beyond
AU - Atwood, Jerry L.
AU - Barbour, Leonard J.
AU - Hardie, Michaele J.
AU - Raston, Colin L.
PY - 2001/1/1
Y1 - 2001/1/1
N2 - The main focus of this review is the self-assembly in aqueous solutions of bowl-shaped sodium p-sulfonatocalix[4,5]arenes with main group, transition metal and lanthanoid species, and with various organic molecules as additional supramolecular building components, for example 18-crown-6, and other macrocycles, pyridine N-oxide, amino-acids, and more. The versatility of building up new materials based on these components is demonstrated by the formation of a diverse range of complex inclusion structures assembled through π-stacking, hydrogen bonding and coordination interactions. There are up-down arrangements of calix[4]arenes in hydrophobic-hydrophobic bi-layer structures with the positively charged species and included molecules between the layers. A variant of this is prevalent in structures incorporating 18-crown-6 which, in essence, are built up of globular superanions or ionic capsules, for example {Na+ ⊂ (18-crown-6)(H2O)n} ⊂ {(p-sulfonatocalix[4]arene4-)2}7-, n = 0 or 2. These can crystallize, often selectively, polynuclear hydrolytic M(III) cations [M2(OH)2(H2O)8]4+, [M3(OH)4(H2O)10]5+, [M4(OH)6(H2O)12]6+, M = Cr or Rh, or [Al13O4(OH)24(H2O) 12]7+, depending on the pH and other synthetic parameters. Lanthanide(III) ions form a range of complexes at specific pH in the presence of the calixarene and crown ether, including complexes containing the capsule [{18-crown-6} ⊂ ((M(H2O)7 3+ )1.33(p-sulfonatocalix[4]arene4-)}2], for the smaller lanthanides, or the Ferris-wheel type structure [{La3+ ⊂ (18-crown-6)(OH2)3} ∩ {(p-sulfonatocalix[4]arene4- + 2H+)}]+, for the larger lanthanide. In the presence of pyridine N-oxide, at pH 4 where the calixarenes take on 5 - charge, an up-up arrangement of sulfonated calixarenes results, either assembled in icosahedral spheres, or infinite chiral, helical nano-tubes.
AB - The main focus of this review is the self-assembly in aqueous solutions of bowl-shaped sodium p-sulfonatocalix[4,5]arenes with main group, transition metal and lanthanoid species, and with various organic molecules as additional supramolecular building components, for example 18-crown-6, and other macrocycles, pyridine N-oxide, amino-acids, and more. The versatility of building up new materials based on these components is demonstrated by the formation of a diverse range of complex inclusion structures assembled through π-stacking, hydrogen bonding and coordination interactions. There are up-down arrangements of calix[4]arenes in hydrophobic-hydrophobic bi-layer structures with the positively charged species and included molecules between the layers. A variant of this is prevalent in structures incorporating 18-crown-6 which, in essence, are built up of globular superanions or ionic capsules, for example {Na+ ⊂ (18-crown-6)(H2O)n} ⊂ {(p-sulfonatocalix[4]arene4-)2}7-, n = 0 or 2. These can crystallize, often selectively, polynuclear hydrolytic M(III) cations [M2(OH)2(H2O)8]4+, [M3(OH)4(H2O)10]5+, [M4(OH)6(H2O)12]6+, M = Cr or Rh, or [Al13O4(OH)24(H2O) 12]7+, depending on the pH and other synthetic parameters. Lanthanide(III) ions form a range of complexes at specific pH in the presence of the calixarene and crown ether, including complexes containing the capsule [{18-crown-6} ⊂ ((M(H2O)7 3+ )1.33(p-sulfonatocalix[4]arene4-)}2], for the smaller lanthanides, or the Ferris-wheel type structure [{La3+ ⊂ (18-crown-6)(OH2)3} ∩ {(p-sulfonatocalix[4]arene4- + 2H+)}]+, for the larger lanthanide. In the presence of pyridine N-oxide, at pH 4 where the calixarenes take on 5 - charge, an up-up arrangement of sulfonated calixarenes results, either assembled in icosahedral spheres, or infinite chiral, helical nano-tubes.
KW - Sodium p-sulfonatocalix[4,5]arenes
KW - Supramolecular building components
UR - http://www.scopus.com/inward/record.url?scp=0034799029&partnerID=8YFLogxK
U2 - 10.1016/S0010-8545(01)00345-9
DO - 10.1016/S0010-8545(01)00345-9
M3 - Review article
AN - SCOPUS:0034799029
SN - 0010-8545
VL - 222
SP - 3
EP - 32
JO - Coordination Chemistry Reviews
JF - Coordination Chemistry Reviews
IS - 1
ER -