Study On Supramolecular Chemistry Of 4-Sulfocalix[n]arene

Supramolecular chemistry is one of the most attractive fields in chemistry, life science and materials science. Calixarenes taken as the third general supramolecular compounds have received particular interest of numerous chemists in recent years.Water-soluble calix[n]arenes, possessing strongly hydrophilic upper and lower rims and a strongly hydrophobic cone-like cavity, have become increasingly important in the field of supramolecular chemistry and crystal engineering in recent decades. As a multifunctional supramolecular synthon, the ubiquitous 4-sulfocalix[n]arene (here after abbreviated as SC[n]A) can form various kinds of supramolecular aggregations which include extended bilayer clay-type structures, molecular capsules, nanometer scale spheres and tubules. The aim of this dissertation is to construct new 4-sulfocalix[n]arene-based coordination complexes. The main contents include the following main points:1) Twelve 4-sulfocalix[4]arene-based metal complexes, namely, H2[(SC[4]A)La(H2O)7]2·2C2H5OH·12H2O (1), [H(SC[4]A)La(H2O)5]n·5nH2O (2), [(SC[4]A)La(H2O)4(NO3)La(H2O)5]n·7nH2O (3), H[(SC[4]A)Mn(H2O)4Mn0.5(H2O)2] }n·6nH2O (4), {NH4[(SC[4]A)Mn(H2O)4Mn0.5(H2O)2]}n·5nH2O (5), [(SC[4]A)Mn2(H2O)8]n·6nH2O (6), (NH4)2{(SC[4]A)[Mn0.5(H2O)2]2}n·6nH2O (7), [H(SC[4]A)La(H2O)5]n·11nH2O (8), [H(SC[4]A)La(H2O)5]n·nC2H5OH·4nH2O (9), [H(SC[4]A)La(H2O)5]n·nC3H7OH·2nH2O (10), [H(SC[4]A)La(H2O)8]·C3H6O·9H2O (11), [H(SC[4]A)La(H2O)4(CH2OHCHOHCH2OH)]2·10H2O (12) were synthesized and structurally characterized. Three La3+/4-sulfocalix[4]arene complexes (1), (2) and (3) were constructed from La3+ and 4-sulfocalix[4]arene in different pH conditions, which exhibits"molecular capsule", two-dimensional and three- dimensional structure respectively, showing clearly the structural response on pH value of the reaction. Three managanese/4-sulfocalix[4]arene complexes (4), (5) and (6) have been synthesized under different pH conditions. Complex (4), which exhibits a one-dimensional (1D) structure, is formed at [H+] = 2 M. Reaction at pH = 4 leads to another one-dimensional (1D) coordination polymer of (5). At pH = 5, a two-dimensional (2D) coordination polymer of complex (6) is formed, showing clearly structural effects on pH response. Five La3+/4-sulfocalix[4]arene complexes (8) to (12) have been synthesized under different solvent conditions. Since the only difference in synthetic condition among complexes (8) to (12) is the solvent of the reactions, it is clear that solvent of the reaction is of key importance in the assembly of La3+/4-sulfocalix[4]arene complex.2) Transition metal complexes inserted into various molecular containers represents a rare phenomenon in supramolecular chemistry. Investigation of these types of compounds is very important, because encapsulation can substantially affect the geometry of the guest, its thermal stability, magnetic and photochemical properties, electrochemical behavior and reactivity. Inclusion into macrocyclic hosts may be the best way to stabilize unusual coordination environments and unstable oxidation states of metals, trap short-living reaction intermediates, and solubilize metal complexes in required reaction media. Here we report syntheses and crystal structure of nine new 4-sulfocalix[4]arene-based transition metal complexes, namely, [(SC[4]A)2K(H2O)2]n·[Co(en)2(H2O)2]n·[Co(H2O)6]n·12nH2O (13), H(SC[4]A)·[Co (en)3]·8H2O (14), H4[(SC[4]A)Cu(C5H6N2)(H2O)3]2·12H2O (15), {(SC[4]A)[Cu(C5H6N2)(H2O)4]2}·7H2O (16), [H(SC[4]A)]2·[Cu(H2O)6]·[Cu(C6H8N2) (H2O)4]2·32H2O (17), [(SC[4]A)2[Cu(C6H8N2)(H2O)4]2Cu(H2O)4]·Cu(H2O)6·8H2O (18), {[H(SC[4]A)]2[Cu(H2O)5]2Cu(H2O)4]}·(C7H10N2)2·12H2O (19), [(2,2'-bpy)Cu(H2O)4]n·[(SC[4]A)(2,2'-bpy)Cu(H2O)2]n·8nH2O (20) and [(SC[4]A)(2,2'-bpy)Cu(H2O)2 (2,2'-bpy)Cu(H2O)3]n·6nH2O (21). The inclusion and self-assembly properties of 4-sulfocalix[4]arene were investigated by these complexes crystal structures.3) Two novel macrocycles interplay with macrocycles supramolecular forms, in which 4-sulfocalix[4]arene and 4-sulfocalix[6]arene interact with cucurbit[6]uril respectively, namely , Q6@SC[4]A·0.5HCl·29H2O (22) and (0.5Q6)2@SC[6]A·6NH4·35.5H2O (23) were synthesized and structurally characterized. The present structures are the striking example of the supramolecular lock/key recognition interactions and the size–shape complementarity between 4-sulfocalix[4,6]arene and cucurbit[6]uril that allows the formation of an efficiently packed two-component system.