以单缺位Keggin结构阴离子为构筑块的3d-4f衍生物的合成、结构及性质研究

题名:以单缺位Keggin结构阴离子为构筑块的3d-4f衍生物的合成、结构及性质研究
作者:陈幻妮
学位授予单位:河南大学
关键词:三斜晶系:7491,Keggin:3392,空间群:2696,合成法:1915,晶体结构:1773,化合物:1660,电化学性质:1619,单斜晶系:1556,晶体学数据:1351,阴离子:1304,荧光性质:1274,稀土:1120,过渡金属:986,荷移跃迁:844,多金属氧簇:817,配位水:740,水热合成:704,八面体构型:501,磷钨酸盐:456,元素分析:454
摘要:
 本论文基于分子设计与组装的思想,结Neodymium magnets合常规水溶液合成和水热合成方法,通过调控反应条件,如pH值、反应温度、时间、反应物浓度及配比等,合成出一系列结构新颖的基于单缺位Keggin结构阴离子的3d-4f衍生物,并对化合物晶体结构、谱学性质(IR、UV)、热性质(TG)、荧光、EPR及电化学性质等进行了研究。
 (1)以单缺位Keggin结构阴离子[α-PW11O39]7为构筑块,成功地合成了两类化合物:稀土二聚衍生物(2:2型)和一维链状(1:1型)稀土衍生物,对化合物的电化学性质和热性质进行了研究。
 (2)利用水热合成方法,向单缺位Keggin结构阴离子[α-PW11O39]7-体系中引入稀土和过渡金属,得到了四个一维锯齿链状、三个二维层状和一个三维框架结构的3d-4f衍生物。
 (3)利用水热合成方法,向单缺位Keggin结构阴离子[α-SiW11O39]8-体系中引入稀土和过渡金属,得到了两个二聚结构、一个一维链状、两个二维层状和三个三维框架结构的衍生物。
 (4)合成了两个基于饱和Keggin结构阴离子的多金属氧簇化合物,对化合物的荧光性质及热性质进行了研究。化合物的组成和晶体学数据如下:
 1. [(CH3)4N]4[PW11O39H2La(H2O)4]2·3H2O:三斜晶系,P-1空间群,a = 13.5383(10) , b = 16.0687(12), c = 18.6958(13) ,α= 65.9630(10)°,β= 83.1650(10)°,γ= 83.6780(10)°, V = 3679.5(5) 3, Z = 1, R1 = 0.0589, wR 2 = 0.1447;
 2. [(CH3)4N]4[(α-PW11O39)Er(H2O)2]2.5H2O:单斜晶系,P2(1)/n空间群,a = 13.5285(10) , b = 23.8787(18) , c = 20.8672(12) ,β= 100.3590(10)°, V = 6631.1(9) 3, Z = 4, R1 = 0.0498, wR2 = 0.1265;
 3. Na3[Cu(en)2]0.5H3{[Cu(en)2]2(H2O)La[(α-PW11O39)2]}7.5H2O:三斜晶系,P-1间群,a = 15.8496(11) , b = 18.1311(13) , c = 21.0962(15) ,α= 113.7740(10)°,β= 90.9780(10)°,γ= 94.3570(10)°, V = 5524.4(7) 3, Z = 2, R1 = 0.0599, wR2 = 0.1581;
 4. Na2[Cu(en)2]0.5H4{[Cu(en)2]2(H2O)Sm[(α-PW11O39)2]}3H2O:三斜晶系,P-1空间群,a = 16.082(15) , b = 18.343(18) , c = 21.21(2) ,α= 114.22(3)°,β= 91.11(4)°,γ= 94.07(4)°, V = 5684(9) 3, Z = 2, R1 = 0.1088, wR2 = 0.2255;
 5. (enH2)2[Cu(en)2]{[Cu(en)2]1.5[Cu(en)(2,2'-bipy)]Ce[(α-PW11O39)2]}2H2O:三斜晶系,P-1空间群,a = 12.923(8) , b = 19.427(13) , c = 21.115(14) ,α= 95.816(11)°,β= 93.135(11)°,γ= 96.147(11)°, V = 5232(6) 3, Z = 2, R1 = 0.0721, wR2 = 0.1353;
 6. (enH2)2[Cu(en)2H2O]{[Cu(en)2]1.5(H2O)[Cu(en)(2,2'-bipy)]Pr[(α-PW11O39)2]} 6.5H2O:三斜晶系,P-1空间群,a = 13.0173(6) , b = 19.3803(9) , c = 21.5028(9) ,α= 96.0070(10)°,β= 95.3110(10)°,γ= 95.7130(10)°, V = 5339.0(4) 3, Z = 2, R1 = 0.0440, wR2 = 0.0866;
 7. [Cu(en)2(H2O)2][Cu(en)(2,2'-bipy)H2O]H{[Cu(en)2]2(H2O)[Cu(en)(2,2'-bipy)] Gd[(α-PW11O39)2]}6H2O:三斜晶系,P-1空间群,a = 13.7083(16) , b = 19.323(2) , c = 25.369(3) ,α= 105.421(2)°,β= 104.048(2)°,γ= 99.871(2)°, V = 6080.8(12) 3, Z = 2, R1 = 0.0639, wR2 = 0.1582;
 8. [Cu(en)2(H2O)2][Cu(en)(2,2'-bipy)(H2O)]H{[Cu(en)2]2(H2O)[Cu(en)(2,2'-bipy)]Tb[(α-PW11 O39)2]}6.5H2O:三斜晶系,P-1空间http://www.chinamagnets.biz/Neodymium/Ball-Neodymium-Magnets.php群,a = 13.7020(8) , b = 19.3240(10) , c = 25.3506(14) ,α= 105.3820(10)°,β= 104.0170(10)°,γ= 99.9580(10)°, V = 6074.0(6) 3, Z = 2, R1 = 0.0441, wR2 = 0.0827;
 9. [Cu(en)2(H2O)][Cu(en)(2,2'-bipy)(H2O)]H{[Cu(en)2]2(H2O)[Cu(en)(2,2'-bipy)] Er[(α-PW11O39)2]}7.5H2O:三斜晶系,P-1空间群,a = 13.7089(13) , b = 19.2704(18) , c = 25.333(2) ,α= 105.130(2)°,β= 104.1910(10)°,γ= 99.847(2)°, V = 6062.6(10) 3, Z = 2, R1 = 0.0381, wR2 = 0.0847;
 10. Na2[Cu(en)2]0.5H5{[(α-PW11O39)2]Nd[Cu(en)2]1.5[Cu(en)(2,2'-bipy)]}:三斜晶系,P-1空间群,a = 15.570(3) , b = 19.830(4) , c = 20.854(4) ,α= 116.113(3)°,β=91.969(4)°,γ= 94.603(4)°, V = 5745(2) 3, Z = 2, R1 = 0.1013, wR2 = 0.2601;
 11. K0.5H1.5(enH2)3[Cu(en)2]1.5(H2O){[Cu(en)2]Dy[α-SiW11O39)2]}·5H2O:单斜晶系,P2(1)/c空间群,a = 17.5614(14) , b = 24.208(2) , c = 24.557(2) ,β= 104.1320(10)°, V = 10123.9(14) 3, Z = 4, R1 = 0.0615, wR2 = 0.1467;
 12. K0.5H1.5(enH2)3[Cu(en)2]1.5(H2O){[Cu(en)2]Eu[α-SiW11O39)2]}·4.5H2O :单斜晶系,P2(1)/c空间群,a = 18.1316(10) , b = 25.0587(14) , c = 25.3116(14) ,β= 104.0260(10)°, V = 11157.6(11) 3, Z = 2, R1 = 0.0606, wR2 = 0.1302;
 13. (enH2)0.5[Cu(en)2]0.5H{[α-SiW11O39)]La[Cu(en)2]}·3H2O:单斜晶系,P2(1)/n空间群,a = 16.6434(9) , b = 13.6944(7) , c = 21.8679(11) ,β= 107.0910(10)°, V = 4764.1(4) 3, Z = 4, R1 = 0.0345, wR2 = 0.0723;
 14. (enH2)0.5[Cu(en)2]0.5H{[α-SiW11O39)]Ce[Cu(en)2]}·2H2O:单斜晶系,P2(1)/n空间群,a = 16.6217(12) , b = 13.6670(10) , c = 21.8926(15) ,β= 106.9950(10)°, V = 4756.1(6) 3, Z = 4, R1 = 0.0372, wR2 = 0.0819;
 15. (enH2)2H4{[Cu(en)2]2.5(H2O)Nd[α-SiW11O39)2]}·7H2O:单斜晶系,P2(1)/n空间群,a = 22.249(2) , b = 11.8530(11) , c = 40.163(4) ,β= 102.051(2)°, V = 10358.2(17) 3, Z = 4, R1 = 0.0460, wR2 = 0.1025;
 16. (enH2)2H3{[Cu(en)2]3(H2O)Pr[α-SiW11O39)2]}·6H2O:单斜晶系,P2(1)/n空间群,a = 21.816(12) , b = 11.667(7) , c = 39.20(2) ,β= 101.698(10)°, V = 9771(10) 3, Z = 4, R1 = 0.0476, wR2 = 0.1070;
 17. (enH2)H3{[Cu(en)2]4(H2O)Sm[α-SiW11O39)2]}·6H2O:单斜晶系,P2(1)/n空间群,a = 22.2470(7) , b = 11.7997(4) , c = 39.9452(13) ,β= 102.2010(10)°, V = 10249.1(6) 3, Z = 4, R1 = 0.0437, wR2 = 0.0972;
 18. [CuII(1,3-dap)2]2[CuII(1,3-dap)]2H[α-PW10.5CuII1.5O40]:单斜晶系,C2/c空间群,a = 26.205(5) , b = 20.583(4) , c = 13.249(3) ,β= 119.166(3)°, V = 6240(2) 3, Z = 4, R1 = 0.0577, wR2 = 0.1315;
 19. [CuI(phen)2]3[α-PW12O40]:三斜晶系,Pī空间群,a = 14.0187(13) , b = 15.5564(14) , c = 20.3800(19) ,α= 83.450(2)°,β= 89.661(2)°,γ= 78.262(2)°, V = 4322.5(7) 3, Z = 2, R1 = 0.0423, wR2 = 0.0965;
学位年度:2010