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全文共分两部分。第一部分通过分子设计与组装,利用稀土金属和羧酸配体的参与,采用常规水溶液合成法制备了15例新型稀土金属构筑的有机-无机多金属氧酸盐,并对它们的晶体结构、谱学性质(IR、UV、XRD)、热性质(TG)、荧光性质进行了表征和研究。I.稀土金属构筑的具有三维框架结构的有机-无机多金属氧酸盐。结构解析表明化合物19基本同构,它们均是由Keggin阴离子[SiW12O40]4–作为模板形成的三维框架结构。荧光测试表明,化合物9具有明显的红色荧光。1. [Tm(pydc)(H2O)3]4[SiW12O40]·4H2O:四方晶系,I4(1)/a空间群,a = 21.751(3) (A|·), b = 21.751(3) (A|·),c = 16.1438(15) (A|·),V = 7637.7(17) (A|·)3,Z = 4,R1 = 0.0320,wR 2 = 0.0700。2. [Y(pydc)(H2O)3]4[SiW12O40]·4H2O:四方晶系,I4(1)/a空间群,a = 21.8154(9) (A|·), b = 21.8154(9) (A|·),c = 16.1967(12) (A|·),V = 7708.2(7) (A|·)3,Z = 4,R1 = 0.0489,wR 2 = 0.1232。3. [Tb(pydc)(H2O)3]4[SiW12O40]·4H2O:单斜晶系,C2/c空间群,a = 30.629(9) (A|·),b = 16.224(4) (A|·),c = 21.792(6) (A|·),β= 134.334(7)°,V = 7746(4) (A|·)3,Z = 4,R1 = 0.0710,wR2 = 0.1822。4. [Dy(pydc)(H2O)3]4[SiW12O40]·4H2O:四方晶系,I4(1)/a空间群,a = 21.776(4) (A|·), b = 21.776(4) (A|·),c = 16.138(5) (A|·),V = 7653(3) (A|·)3,Z = 4,R1 = 0.0707,wR 2 = 0.1838。5. [Gd(pydc)(H2O)3]4[SiW12O40]·4H2O:单斜晶系,C2/c空间群,a = 30.487(2) (A|·),b = 16.3460(9) (A|·),c = 21.8505(13) (A|·),β= 134.24°,V = 7801.6(8) (A|·)3,Z = 4,R1 = 0.0518,wR2 = 0.1227。6. [Pr(pydc)(H2O)4]4[SiW12O40]·4H2O:四方晶系,I4(1)/a空间群,a = 21.9314(10)(A|·),b = 21.9314(10) (A|·),c = 16.7059(15) (A|·),V = 8035.3(9) (A|·)3,Z = 4,R1 = 0.0309,wR 2 = 0.0669。7. [La(pydc)(H2O)4]4[SiW12O40]·4H2O:四方晶系,I4(1)/a空间群,a = 21.9285(8) (A|·), b = 21.9285(8) (A|·),c = 16.7265(12) (A|·),V = 8043.1(7) (A|·)3,Z = 4,R1 = 0.0247,wR 2 = 0.0521。8. [Sm(pydc)(H2O)4]4[SiW12O40]·4H2O:四方晶系,I4(1)/a空间群,a = 21.685(5) (A|·), b = 21.685(5) (A|·),c = 16.470(7) (A|·),V = 7745(4) (A|·)3,Z = 4,R1 = 0.0311,wR 2 = 0.0726。9. [Eu(pydc)(H2O)4]4[SiW12O40]·4H2O:四方晶系,I4(1)/a空间群,a = 21.7777(7) (A|·), b = 21.7777(7) (A|·),c = 16.4167(10) (A|·),V = 7785.9(6) (A|·)3,Z = 4,R1 = 0.0300,wR 2 = 0.0714。II.稀土金属构筑的具有二维层状结构的有机-无机多金属氧酸盐。在化合物10中,杂多阴离子[SiW12O40]4–通过端氧原子连接稀土配离子,形成具有(4, 4)–连接的二维拓扑结构。10. [Y(pydc)(H2O)3]2H2[SiW12O40]·4H2O:正交晶系,Pnma空间群,a = 25.792(2) (A|·), b = 16.3573(13) (A|·),c = 13.6352(11) (A|·),V = 5752.5(8) (A|·)3,Z = 4,R1 = 0.0415,wR 2 = 0.0878。III.稀土金属构筑的具有一维链状结构的有机-无机多金属氧酸盐。在化合物11和12中,稀土离子通过3, 4–吡啶二羧酸配体的桥联作用形成一维链状结构,杂多阴离子又通过弱的K–O键与稀土配离子链相连构成二维层。11. {[Pr(H2O)3][K(H2O)2](pydc)2}2H4[SiW12O40]·2H2O:三斜晶系,P–1空间群,a = 10.8200(11) (A|·),b = 11.1094(12) (A|·),c = 16.9290(17) (A|·),α= 80.845(2)°,β= 79.699(2)°,γ= 61.9120(10)°,V = 1759.7(3) (A|·)3,Z = 1,R1 = 0.0464,wR 2 = 0.1150。12. {[Nd(H2O)3][K(H2O)2](pydc)2}2H4[SiW12O40]·2H2O:三斜晶系,P–1空间群,a = 10.848(3) (A|·),b = 11.156(3) (A|·),c = 16.983(4) (A|·),α= 80.890(4)°,β= 79.719(4)°,γ= 62.013(3)°,V = 1779.2(7) (A|·)3,Z = 1,R1 = 0.0494,wR 2 = 0.1218。IV.稀土金属构筑的具有孤立结构的有机-无机多金属氧酸盐。在化合物1315中,杂多阴离子[PMo12O40]3–与稀土配离子通过静电引力作用相结合。13. [Pr(pydc)(H2O)6]2H[PMo12O40]·4H2O:四方晶系,I4(1)/a空间群,a = 15.2194(11) (A|·),b = 15.2194(11) (A|·),c = 28.481(4) (A|·),V = 6597.1(12) (A|·)3,Z = 4,R1 = 0.0673,wR 2 = 0.1673。14. [Nd(pydc)(H2O)6]2H[PMo12O40]·4H2O:四方晶系,I4(1)/a空间群,a = 15.3257(14) (A|·),b = 15.3257(14) (A|·),c = 28.485(5) (A|·),V = 6690.5(14) (A|·)3,Z = 4,R1 = 0.0454,wR 2 = 0.1181。15. [Tb(pydc)(H2O)6]2H[PMo12O40]·4H2O:四方晶系,I4(1)/a空间群,a = 15.2768(16) (A|·),b = 15.2768(16) (A|·),c = 28.337(6) (A|·),V = 6613.2(17) (A|·)3,Z = 4,R1 = 0.0612,wR 2 = 0.1623。第二部分通过分子设计与组装,利用简单原料代替缺位杂多钼酸盐前驱体,采用常规水溶液合成法、扩散法和水热技术制备了6例过渡金属取代的夹心型锗钼酸盐,并对它们的晶体结构、谱学性质(IR、UV、XRD、XPS)、热性质(TG)、表面光电压(SPS)、磁性质进行了表征和研究。I.过渡金属取代的双核夹心型锗钼酸盐。SPS和EFISPS测试表明化合物16表现出了n-型半导体特性,磁性测试表明化合物16显示了反铁磁性相互作用。16. [Na12(H2O)36][Cu2(β–Y–GeMo9O33)2]·3H2O :三斜晶系, P–1空间群, a = 13.2369(8) (A|·),b = 13.5286(8) (A|·),c = 16.6405(13) (A|·),α= 73.2850(10)°,β= 66.56°,γ= 60.71°,V = 2368.4(3) (A|·)3,Z = 1,R1 = 0.0327,wR 2 = 0.0862。17. [N(CH3)4]4[Na6(H2O)24][Cr2(β–Y–GeMo9 O33)2]·7H2O:三斜晶系,P–1空间群,a = 13.3571(12) (A|·),b = 13.5019(12) (A|·),c = 18.4660(17) (A|·),α= 76.9310(10)°,β= 77.5830(10)°,γ= 61.0300(10)°,V = 2816.3(4) (A|·)3,Z = 1,R1 = 0.0249,wR 2 = 0.0745。18. [Cu(en)2]2[Cu(en)2(H2O)]2{[Cu(en)2]2[Cu2(β–Y–GeMo9O33)2]}·8H2O:三斜晶系,P–1空间群,a = 13.0503(14) (A|·),b = 14.0662(15) (A|·),c = 17.4386(19) (A|·),α= 79.750(2)°,β= 73.805(2)°,γ= 64.567(2)°,V = 2770.0(5) (A|·)3,Z = 2,R1 = 0.0506,wR 2 = 0.1398。II.过渡金属取代的四核夹心型锗钼酸盐。SPS和EFISPS测试表明化合物19表现出了n-型半导体特性,磁性测试表明化合物19表现出了铁磁性相互作用。19. [Na11(H2O)25]H[Ni4(H2O)2(α–B–GeMo9O34)2]·6H2O:三斜晶系,P–1空间群,a = 11.6135(8) (A|·),b = 12.8737(9) (A|·),c = 17.1160(17) (A|·),α= 97.3750(10)°,β= 107.0050(10)°,γ= 111.6240(10)°,V = 2193.2(3) (A|·)3,Z = 1,R1 = 0.0332,wR 2 = 0.0911。20. [Na11(H2O)25]H[Mn4(H2O)2(α–B–GeMo9O34)2]·6H2O:三斜晶系,P–1空间群,a = 11.6756(10) (A|·),b = 12.9056(11) (A|·),c = 17.3437(15) (A|·),α= 97.3770(2)°,β= 106.8390(10)°,γ= 111.8450(10)°,V = 2238.1(3) (A|·)3,Z = 1,R1 = 0.0547,wR 2 = 0.1338。21. [Na11(H2O)25]H[Co4(H2O)2(α–B–GeMo9O34)2]·6H2O:三斜晶系,P–1空间群,a = 11.584(3) (A|·),b = 12.856(4) (A|·),c = 17.173(7) (A|·),α= 97.380(6)°,β= 106.906(6)°,γ= 111.713(4)°,V = 2191.7(13) (A|·)3,Z = 1,R1 = 0.0601,wR 2 = 0.1672。