| A number of calixarene derivatives containing pherpheral groups have been synthesized due to the ready modification at the lower-rim or the upper-rim of calixarenes. These derivatives have displayed potential broad applications in material science, separation technology, biomimetics and biological science. So far, plenty of studies have been devoted to assembly of main group, transition or lanthanide metals with the p-sulfonatocalix[4]arenes. However, studies engaged in calix[4]arenes containing trimethylammonium or carboxylate groups are quite rare. In this thesis, we have designed and synthesized two kinds of calix[4]arenes ligands with trimethylammonium or carboxylate groups and carried out their reactions with transition or lanthanide metals. A series of matal complexes were prepared by changing ligands and the reaction conditions, which were briefly described as follows.1. Reaction of 5,11,17,23-tetramino-25,26,27,28-tetrahydroxy-calix[4]arene （1） with MeI and NaOAc·3H2O in DMF produced [H4L]I4 （2） {H4L = [5,11,17,23-tetrakis（trimethylammonium）-25,26,27,28-tetrahydroxycalix[4]arene]}. Anion exchange of 2 with [Ag（MeCN）4]（PF6） in MeCN afforded [H4L]（PF6）4 （3）, which was recrystallized in MeCN/MeOH to form crystals of [H3L]（PF6）3·MeOH·2MeCN （3a）. Further treatment of 3 with Mn（OAc）2·4H2O in MeOH/MeCN produced [Mn（III）L（O2）（H2O）]（PF6）2 （4）. 4 has a bowl-shaped cationic structure with a D4d symmetry in which the central Mn（III） atom is linked by a zwitterionic ligand L through four O atoms. The octahedral Mn center is further loosely coordinated by two O atoms from H2O and O2?. The superoxo ion is firstly introduced into this Mn（III）-calix[4]arene complex in an end-on fashion and the Mn?O2 species shows an unprecedented linear arrangement. 4 exhibited a highly efficient catalytic activity towards epoxidation of alkenes with molecular oxygen plus isobutyraldehyde under mild conditions. The region-selectivity of epoxidation for either trans-alkene or cis-alkene was excellent.2. Treatment of a tetracationic calix[4]arene [H4L][PF6]4 （H4L = [5,11,17,23-tetrakis（trimethylammonium）-25,26,27,28-tetrahydroxycalix[4]arene]） （3） with Na2CO3 or NaHCO3 afforded a mono-deprotonated complex [H3L][PF6]3·MeCN （5·MeCN）. Similar reactions of 3 with NaNO3, Zn（NO3）2 or Cu（NO3）2 gave rise to an anion exchange product [（H3L）2{（NO3）6（H2O）6}]·4MeCN （6·4MeCN）. 5·MeCN contains a 3D cationic H-bonded [H3L]3n+ net in which PF6? anions are embedded into its 1D channels. 6·4MeCN consists of a 3D cationic H-bonded [H3L]n3n+ net in which novel four-clawed crown-like nitrate-water cluster [（NO3）6（H2O）6]6- anions are included into its cavities formed by hydrogen interactions of four [H3L]3+ cations.3. Reaction of 25,26,27,28-tetrahydroxy-calix[4]arene with 4 equiv. of m-carboxybenzenediazonium chloride in the presence of NaOAc·3H2O in DMF produced a new azo calix[4]arene [H4L] （7, H4L = 5,11,17,23-tetrakis[（m-carboxyphenyl）azo]-25,26,27,28-tetrahydroxycalix[4]arene）. Hydrothermal reactions of Cd（NO3）2·4H2O with H4L at 90°C under pH = 2.03.0 or 5.06.0 gave rise to two coordination polymers {[H3O]2[Cd3L2（DMF）3]·2EtOH}n （8） and {[H3O]2[Cd7L4（DMF）4（EtOH）2（H2O）2]·5DMF·11.5EtOH·H2O}n （9）. Solvothermal reactions of LnCl3·6H2O （Ln = Nd, Eu, Yb） with equimolar H4L at 90°C or 140°C gave rise to a set of six lanthanide（III） coordination polymers {[Nd2ClL（HCOO）（DMF）3（H2O）]·0.5DMF·MeCN·1.5H2O}n （10）, {[Ln2ClL（HCOO）（DMF）]·sol}n （11: Ln = Eu, sol = 0.5MeCN·1.5H2O; 12: Ln = Yb, sol = 1.5H2O） and {[H3O][LnL（H2O）]·DMF·MeCN·H2O}n （13: Ln = Nd; 14: Ln = Eu; 15: Ln = Yb）. 8 holds an intriguing 2D framework. 9 consists of a 3D framework with an unprecedented （3346526371）（364135861） topology. 10?12 have intriguing 2D networks based on [Ln6Cl4L2] units. 13?15 exhibit two-fold interpenetrating 2D networks based on spiral [Ln4L（H2O）4] units. The structural diversities of these frameworks may be greatly affected by pH values and temperatures.4. Treatment of 5,11,17,23-tetrakis[（p-carboxyphenyl）azo] -25,26,27,28-tetrahydroxycalix[4]arene （16, H4L） with HCl in DMF produced 16·4DMF. Reactions of H4L with Cd（NO3）2, LaCl3 and PbX2 （X = NO3, Cl, Br, I） produced six coordination polymers [（Cd4L2）·（DMF）·2H2O]n （17）, [（H3O）5（LaL2）·2DMF]n （18）, {[Pb2L（DMF）4]·2DMF}n （19）, {[H3O]4[Pb4L2（μ2-X）4]·DMF·3H2O}n （20: X = Cl, 21: X = Br）, {[Pb9L2I2（μ2-I）（μ3-I）4（μ4-I）3（H2O）4]·（DMF）·3H2O}n （22）. The intra- and intermolecular hydrogen-bonding interactions and theπ···πinteractions in 16·4DMF form a 2D hydrogen-bonded wavelike network. 17, 18, 20 and 22 have intriguing 2D networks based on [M4L2] units. 16 had a unique reversible color change in a wide pH range from 1 to 13.5. The NLO performances of 19?22 were also studied. |
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