摘要
本论文利用超分子自组装方法设计合成了有序性的超分子粉末型和层层组装薄膜型金属配合物。对它们的磁性能进行了研究，并进一步探索了配合物结构及其内部金属离子有序性与磁性能的关系，为制备具有较强铁磁性的有机材料提供一种新的方法。
论文的主要工作是制备了联噻唑环、吡啶环、邻菲咯啉环三种不同类型的超分子粉末型和多层薄膜型金属配合物。超分子粉末在溶液中制得，多层膜则是以高密度聚乙烯HDPE为基底以配位相互作用为主要推动力经层层自组装得到。通过FT-IR、~1H NMR、UV-vis、AFM、元素分析等测试方法对单体、聚合物、超分子粉末以及多层膜进行了表征，采用EDTA络合滴定和等离子体发射光谱仪测定了超分子粉末及多层膜中的金属含量。
磁性能测试结果表明，对于联噻唑类的配合物，经两种不同的方法制得的超分子粉末及多层膜虽然具有类似的组分及内部结构，其磁性能却完全不同。在超分子粉末型配合物中，除DABT／PAA-Cu~(2+)和DABT-Fe~(2+)／PAA是亚铁磁体外，其余均为较好的铁磁体。联噻唑类薄膜型配合物均显示很好的铁磁性，其磁滞回线表现为典型的S形。对于含Cu~(2+)的薄膜，(DABT／Cu~(2+)／PAA)_(15×2)和(PAA／DABT)_(20×2)-Cu~(2+)不仅具有比相应超分子粉末型配合物高2-4倍的相对磁饱和强度(M_s)，其顺磁居里-外斯温度(θ)的增大幅度也超过5倍。更突出的是，膜(PAA／DABT)_(20×2)-Ni~(2+)的相对磁饱和强度可以达到37.3emu.g~(-1)，膜(DABT／Ni~(2+)／PAA)_(15×2)的顺磁居里-外斯温度可以达到242K。
对于含吡啶环的超分子粉末型配合物，除含对位吡啶环类的(PSSCu／P4MAAP)_(powder)为亚铁磁体外，其余均显示铁磁性，并且间位吡啶环类表现出较好的铁磁性，能够在较高的温度就进入磁有序状态。四种含吡啶环组装膜都显示出较强的铁磁性，它们的特征温度(包括进入磁有序状态的温度、磁相达到饱和的温度以及从顺磁性向铁磁性转换的温度)都高于超分子粉末型配合物。其中，膜(PSSCu／P3MAAP)_(20×2)具有最高的顺磁居里-外斯温度212K，而膜(PSSNi／P4MAAP)_(20×2)具有最高的相对磁饱和强度8.79emu.g~(-1)。
着重研究了含有邻菲咯啉环的多层膜体系的磁性能。随着组装层数的增加，膜的顺磁居里-外斯温度显示出不断增大的趋势；磁滞回线的S形越来越明显，相对磁饱和强度的值也越来越大。随着耦合作用的不断增强，膜的表观磁性能经历了抗磁性、温控磁转换到铁磁性的变化。不论是含Cu~(2+)或Ni~(2+)，多层膜(PSSCu／PMPMA)_(20×2)和(PSSNi／PMPMA)_(20×2)都具有比相应超分子粉末型配合物较高的顺磁居里-外斯温度和较高的相对磁饱和强度。
本文研究还发现，含有P3MAAP、P4MAAP及PMAMP的超分子粉末型或薄膜型配合物的相对磁饱和强度要小于含有DABT的相应超分子粉末型或薄膜。主要是因为与含有小分子组分DABT的体系相比，前面两类体系所用到的组分PSS、P3MAAP、P4MAAP及PMAMP都是分子量相对较高的聚合物，这便使得物质的质量有很大增加，从而引起相对磁饱和强度的值下降。
The main content of this paper is the preparation of novel ordered organic supramolecularpowdered and layer-by-layer multilayer thin-filmed metal complexes based on the self-assemblyapproach, and the study of their magnetic behaviors. The aim is quest for the relationship of thestructure of polymer, the kind of metal ions and the magnetic property of the correspondingcomplex. The studies of the magnetic properties of these multilayer films and supramolecularpowders will not only contribute to the research concerning the relationship of structure andmagnetism, but also provide some useful information for the novel functional materials withelectric and magnetic properties.
Three kinds of polymers, which containing bithiazole ring, pyridine ring or phenanthrolinering, have been synthesized in this paper. The coordinated supramolecules and correspondingmultilayer films, such as DABT/PAA-M~(2+), DABT-Ni~(2+)/PAA, (PAA/DABT)_(20×2)-M~(2+),(DABT/M~(2+)/PAA)_(15×2), (PSSM/P3MAAP)_(powde), (PSSM/P4MAAP)_(powder), (PSSM/P3MAAP)_(20×2),(PSSM/P4MAAP)_(20×2), (PSSM/PMPMA)_(powder) and (PSSM/PMPMA)_(20×2) have been prepared bythe self-assembly method. The multilayer films were obtained on the HDPE substrate, while thesupramolecules were prepared in solutions. The structures of the molecule, polymers,supramolecules and multilayer films were determined by FT-IR、~1H NMR、UV-vis、AFM andelemental analysis. The metal contents were measured by complexometric titration andinductively coupled plasma emission spectrometer (ICP).
The magnetic properties of these materials were measured by a PPMS-9T magnetometer(QUANTUM DESIGN), which include magnetization versus temperature, magnetization versusapplied field, magnetic susceptibility versus temperature and magnetic hysteresis. Themeasurement results reveal that the system containing bithiazole rings displayed differentmagnetic behaviours not only for the supramolecules but also for the multilayer films, althoughthe component and structure are similar. Most of the supramolecular powders are softferromagnet, except that DABT/PAA-Cu~(2+) and DABT-Fe~(2+)/PAA exhibit special ferrimagneticproperties. All multilayer films display strong ferromagnetic properties with typical "S" shape of the hysteresis loop. For the system containing copper ions, the relative saturation magnetization(M_s) of the multilayer films (DABT/Cu~(2+)/PAA)_(15×2) and (PAA/DABT)_(20×2)-Cu~(2+) is about 2-4times as high as that of the corresponding supramolecular powders, and the value ofCurie-Weiss temperature also increases more than 5 times. The film (DABT/Ni~(2+)/PAA)_(15×2) showhigh specific magnetization, up to Curie-Weiss temperature (θ=242 K). It is noteworthy that afairly high value of relative saturation magnetization (M_s=37.3 emu.g~(-1)) is observed for the film(PAA/DABT)_(20×2)-Ni~(2+).
In the pyridine system, for the bulk supramolecular powders, (PSSNi/P3MAAP)_(powder) and(PSSCu/P3 MAAP)_(powder) display better ferromagnetic behaviours, while the(PSSCu/P4MAAP)_(powder) is a ferrimagnet. And the temperature of the magnetic order phase forthe powders containing P3MAAP is higher than others, which coule be attributed to the differentcoordinated structure. All films display strong soft ferromagnetic properties, and thecharacteristic temperature, including the temperature of the magnetic order phase, thetemperature of the magnetic saturation phase and the temperature of the magnetic trasition phase,is higher than those of the corresponding supramolecules. It is found that the multilayer film(PSSNi/P4MAAP)_(20×2) exhibits a fairly high value of relative saturation magnetization (M_s=8.79emu.g~(-1)), while the film (PSSCu/P3MAAP)_(20×2) shows a high Curie-Weiss temperature (θ=212K).
The PSSM/PMPMA multilayer films exhibit a self-improvement behavior with the increasingnumbers of cycles of deposition. The increasingly enhanced magnetic property mainly lies inthree aspects: the relative saturation magnetization, Curie-Weiss temperature and S shapehysteresis loop. It is noteworthy that the relative saturation magnetization (M_s=9.6 emu.g~(-1)) ofthe multilayer film (PSSNi/PMPMA)_(20×2) was about 30 times as high as that of the film(PSSNi/PMPMA)_(3×2). The differences observed in the magnetic ordering temperature reflect thespecific structural arrangements of the compounds on the substrate surface. Such behavior ismainly caused by the stronger ferromagnetic interactions among paramagnetic spins in theregular three-dimensional framework than in planar structure.With the increasing number ofassembled bilayer, the multilayer films show different magnetic properties, which changes from diamagnetic property, magnetic switch with a transition temperature to ferromagnetic property.The system containing Ni~(2+) displays higher relative saturation magnetization and lowerCurie-Weiss temperature, not only for the supramolecules but also for the multilayer films. Forthe twenty bilayers film (PSSCu/PMPMA)_(20×2) and (PSSNi/PMPMA)_(20×2), the relative saturationmagnetization and Curie-Weiss temperature are both higher than those of the bulksupramolecular powders (PSSCu/PMPMA)_(powder) and (PSSNi/PMPMA)_(powder).
By comparing the magnetic properties of all the systems, we can also find that the relativesaturation magnetization of the supramolecules and films containing P3MAAP, P4MAAP andPMAMP is discovered at high level, even higher than the previous report, but the value is lowerthan that of the supramolecules and multilayer films containing DABT, coming from the highmolecular weigh of the PSS, P3MAAP, P4MAAP and PMPMA.
引文
1．何天白，胡汉杰．《功能高分子与新技术》．化学工业出版社，2001．
2. McConnell, H. M. Ferromagnetism in solid free radicals. J. Chem. Phys. 1963, 39, 1910.
3. Mataga, N. Possible ferromagnetic status of some hypothetical hydrocarbons. Theor. Chim.Acta 1968, 10, 372.
4. Ovchinnikov A. A. Multiplicity of the ground state of large alternant organic molecules with conjugated bonds. Theor. Chim. Acta 1978, 47 (4), 297-304.
5. Miller, J. S., Epstein, A. J., Reiff, W. M. Molecular organic ferromagnets. Science 1988, 240,40-47.
6．顾振军，王寿泰．《聚合物的电性和磁性》．上海交通大学出版社，1991．
7．钟文定．《铁磁学》中册．科学出版社．1987．
8. Moskowit, B. M. Hitchhiker's Guide to Magnetism available from:http://www.geo.umn.edu/orgs/irm/hg2m/hg2m_index.html.
9．戴道生，钱昆明．《铁磁学》上册．科学出版社，2000．
10．姜寿亭，李卫．《凝聚态磁性物理》．科学出版社，2003．
11．宛德福，马兴隆．《磁性物理学》(修订本)．第一版．电子科技大学出版社，1999．
12．近角聪信，黄锡成，金龙焕．《磁性体手册》(中译版)．(杨膺善，韩俊德译)．冶金出版社，1984．
13. Cullity, B. D. Introduction to magnetic materrials. Addison-Wesley, California, 1972.
14．郭军，王新伟，李青山，邢丽华，麻晓雷．磁性高分子复合材料的现状与发展．化工时刊2003，17(1)．22-25．
15．丁小斌，孙宗华，万国祥．磁性高分子微球的制备和应用研究进展．化学通报1997，1，1-6．
16．张军华，刘学涌，丁小斌，彭宇行．功能高分子材料载体在检测诊断中的应用．高分子通报2001，5．39-43．
17．陶长元，吴玲，杜军，迟海声．磁性高分子材料的研究及应用进展．材料导报2003，17(4)．50-53．
18. Korshak, Y. V., Medvedeva, T. V., Ovchinnikov, A. A., Spector, V. N. Organic polymer ferromagnet. Nature 1987, 326, 370-372.
19. Cao, Y., Wang, P., Hu, Z. Y, Li, S. Z., Zhang, L. Y, Zhao, J. G.. Chemical and magnetic characterization of organic ferromagnet-poly-BIPO. Synth. Met. 1988, 27, B625-B630.
20. Ovchinnikov, A. A. Abdurakhmanv, U., Kuznetsov, A. A., Magrupov, M. A., Spector, V. N.Pyropolymeric organic ferromagnet. Dokl. Akad. Nauk SSSR 1988, 302, 885-889.
21. Takahashi, M., Turek, P., Nakazawa, Y, Tamura, M., Nozawa, K., Shiomi, D., Ishikawa, M.,Kinoshita, M. Discovery of a quasi-1D organic ferromganet, p-NPNN. Phys. Rev. Lett. 1991,67, 746-748.
22. Tamura, M., Nakazawa, Y, Shiomi, D., Nozawa, K., Hosokoshi, Y, Ishikawa, M., Takahashi M., Kinoshita, M. Bulk ferromagnetism in the β-phase crystal of the p-nitrophenyl nitronyl nitroxide radical. Chem. Phys. Lett. 1991, 186, 401-404.
23. Chiarelli, R., Novak, M.A., Rassat, A., Tholence, J. L. A ferromagnetic transition at 1.48 K in an organic nitroxide. Nature 1993, 363, 147-149.
24. Rajca, A., Pink, M., Rojsajjakul, T., Lu, K., Wang, H., Rajca, S. X-ray crystallography and magnetic studies of a stable macrocyclic tetranitroxide. Intramolecular dimer of nitroxide in a constrained geometry of the upper rim of calix[4]arene. J. Am. Chem. Soc. 2003, 125.8534-8538.
25. Rajca, A., Mukherjee, S., Pink, M., Rajca, S. Exchange coupling mediated through-bonds and through-space in conformationally constrained polyradical scaffolds: calix[4]arene nitroxide tetraradicals and diradical. J. Am. Chem. Soc. 2006, 128, 13497-13507.
26. Rajca, A., Pink, M., Mukherjee, S., Rajca, S., Das, K. 1,3-Alternate calix[4]arene nitronyl nitroxide tetraradical and diradical: synthesis, X-ray crystallographyl, paramagnetic NMR spectroscopy, EPR spectroscopy, and magnetic studies. Tetrahedron 2007, 63, 10731-10742.
27. Nakamura, N., Inoue, K., Iwamura, H. A branched-chain nonacarbene with a nonadecet ground-state-a step nearer to superparamagnetic polycarbenes. Angew. Chem. Int. Ed. Engl.1993, 32, 872-874.
28. Nakamura, N., Inoue, K., Iwamura, H., Fujioka, T., Sawaki, Y. Synthesis and characterization of a branched-chain hexacarbene in a tridecet ground state. An approach to superparamagnetic polycarbenes. J. Am. Chem. Soc. 1992, 114, 1484-1485.
29. Matsuda, K., Nakamura, N., Takahashi, K., Inoue, K., Koga, N., Iwamura, H. Design,synthesis, and characterization of 3 kinds of pi-cross-conjugated hexacarbenes with high-spin (S=6) ground-states. J. Am. Chem. Soc. 1995, 117, 5550-5560.
30. Matsuda, K., Nakamura, N., Inoue, K., Koga, N., Iwamura, H. Design and synthesis of a"starburst"-type nonadiazo compound and magnetic characterization of its photoproduct.Chem. Eur. J. 1996, 2, 259-264.
31.Rajca, A., Lu, K., Rajca, S. High-spin polyarylmethyl polyradical: Fragment of a macrocyclic 2-strand based upon calix[4]arene rings. J. Am. Chem. Soc. 1997, 119,10335-10345.
32. Rajca, A., Wongsriratanakul, J., Rajca, S. Organic spin clusters: Ferromagnetic spin coupling through a biphenyl unit in polyarylmethyl tri-, penta-, hepta-, and hexadecaradicals.J. Am. Chem. Soc. 1997, 119, 11674-11686.
33. Rajca, A., Rajca, S. Intramolecular antiferromagnetic vs ferromagnetic spin coupling through the biphenyl unit. J. Am. Chem. Soc. 1996, 118, 8121-8126.
34. Rajca, A., Wongsriratanakul, J., Rajca, S., Cemy, R. A dendritic macrocyclic organic polyradical with a very high spin of S=10. Angew. Chem. Int. Ed. 1998, 37, 1229-1232.
35. Rajca, A., Rajca, S., Wongsriratanakul, J. Very high-spin organic polymer: pi-conjugated hydrocarbon network with average spin of S ＞= 40. J. Am. Chem. Soc. 1999, 121, 6308.
36. Dougherty, D. A. Spin control in organic molecules. Acc. Chem. Res. 1991,24, 88-94.
37. Iwamura, H., Koga, N. Studies of organic di-, oligo-, and polyradicals by means of their bulk magnetic properties. Acc. Chem. Res. 1993, 26, 346-351.
38. Rajca, A. Oraganic diradicals and polyradicals-from spin coupling to magnetism. Chem. Rev.1994, 94, 871-893.
39. Matsuda, K., Nakamura, N., Inoue, K., Koga, N., Iwamura, H. Toward dendritic two-dimensional polycarbenes: Syntheses of 'starburst'-type nona- and dodecadiazo compounds and magnetic study of their photoproducts. Bull. Chem. Soc. Jpn. 1996, 69, 1483-1494.
40. Nishide, H., Miyasaka, M., Tsuchida, E. Average octet radical polymer: A stable polyphenoxyl with star-shaped pi conjugation. Angew. Chem. Int. Ed. 1998, 37, 2400-2402.
41. Anderson, K. K., Dougherty, D. A. An improved model for one-dimensional polaronic ferromagnetism: electrochemically doped poly(m-phenylenefuchsone). Adv. Mater. 1998,10, 688-692.
42. Bushby, R. J., Gooding, D. Higher-spin pi multiradical sites in doped polyarylamine polymers. J. Chem. Soc., Perkin Trans. 2 1998, 1069-1076.
43. Itoh, K., Takui, T., Teki, Y., Kinoshita, T. Spin alignment in a model-compound of organic ferrimagnets. Mol. Cryst. Liq. Cryst. 1989, 176, 49-65.
44. Dvolaitzky, M., Chiarelli, R., Rassat, A. Stable N,N'-di-tert-butyl-mata-phenylene-bisnitroxides-unexpected ground-state singlets. Angew. Chem. Int. Ed. Engl. 1992, 31,180-181.
45. Rajca, A., Rajca, S. Alkyl-substituted Schlenk hydrocarbon diradicals with triplet and singlet ground states in frozen solutions. J. Chem. Soc., Perkin Trans. 2 1998, 1077.
46. Rajca, A., Wongsriratanakul, J., Rajca, S. Magnetic ordering in an organic polymer. Science 2001, 16, 1503-1505.
47. Allemand, P. M., Khemani, K. C., Koch, A., Wudl, F., Holczer, K., Donovan, S., Gr(u|¨)ner, G.,Thompson, J. D. Organic molecular soft ferromagnetism in a fullerene C_(60). Science 1991.253, 301-303.
48. Tanaka, K., Zakhidov, A. A., Yoshizawa, K., Okahara, K., Yamabe, T., Yakushi, K., Kikuchi,K., Suzuki, S., Ikemoto, I., Achiba, Y. Magnetic properties of TDAE-C_(60) and TDAE-C_(70),where TDAE is tetrakis (dimethylamino) ethylene. Phys. Rev. B 1993, 47, 7554-7559.
49. Mrzel, A., Omerzu, A., Umek, P., Mihailovi(?), D., Jagli(?)i(?), Z., Trontelj, Z. Ferromagnetism in a cobaltocene-doped fullerene derivative below 19 K due to unpaired spins only on fullerene molecules. Chem. Phys. Lett. 1998, 298,329-334.
50. Umek, P., Omerzu, A., Mihailovi(?), D., Tokumoto, M. Synthesis and magnetic characterisation of fullerene derivative based ferromagnets 1-(3-nitro)- and 1-(3-aminophenyl)-1H methanofullerene doped with cobaltocene. Chem. Phys. 2000, 253,361-366.
51. Mihailovic, D., Arcon, D., Venturini, P., Blinc, R., Omerzu, A., Cevc, P. Orientational and magnetic ordering of buckyballs in TDAE-C_(60). Science 1995, 268,400-402.
52. Venturini, P., Mihailovi(?), D., Blinc, R., Cevc, P., Dolin(?)ek, J., Abrami(?), D., Zalar, B., Oshio,H., Allemand, P. M., Hirsch, A., Wudl, F. Magnetic resonance investigation of the magnetic transition in TDAE-C_(60). Int. J. Mod. Phys. B 1992, 6, 3947-3951.
53. Cevc, P., Blinc, R., Er(?)en, V., Ar(?)on, D., Zalar, B., Mihailovi(?), D., Venturini, P. Zero and low field ESR of the magnetic transition in TDAE-C_(60). Solid State Commun. 1994, 90, 543-547.
54. Narymbetov, B., Omerzu, A., Kabanov, V.V., Tokumoto, M., Kobayashi, H., Mihailovic, D.Origin of ferromagnetic exchange interactions in a fullerene-organic compound. Nature 2002, 407, 883-885,
55. Kaul, B. B., Yee, G. Y. A charge-transfer salt magnet based on a non-cyanocarbon acceptor.1,4,9,10-anthracenetetrone and decamethylferrocene. Polyhedron, 2001, 20, 1757-1759.
56. Pokhodnya, K. I., Petersen, N., Miller. J. S. Iron pentacarbonyl as a precursor for molecule-based magnets: formation of Fe[TCNE] (T_c=100 K) and Fe[TCNQ] (Tc = 35 K) magnets. Inorg. Chem, 2002, 41, 1996-1997.
57. Her, J. H., Stephens, P. W., Pokhodnya K. I., Bonner, M., Miller, J. S. Cross-linked layered structure of magnetically ordered [Fe(TCNE)_2]'zCH_2Cl_2 determined by rietveld refinement of synchrotron powder diffraction data. Angew. Chem. Int. Ed. 2007, 46, 1521-1524.
58. Manriquez, J. M., Yee, G. T., McLean, R.S., Epstein, A. J., Miller, J. S. A room temperature molecular/organic-based magnet, Science, 1991,252, 1415-1417.
59. Khasanov, S. S., P(?)rez-Ben(?)tez, A., Narymbetov, B., Zorina, L. V., Shibaeva, R. P.,Singleton, J., Klehe, A. K., Laukhin, V. N., Vidal-Gancedo, J., Veciana, J., Canadell, E.,Rovira C. Interesting transport and magnetic properties in a new family of molecular materials based on the organic donor BET-TTF and the perrhenate anion. J. Mater. Chem.2002, 12 (3), 432-441.
60. Miller, J. S., Calabrese, J. C., McLean, R. S., Epstein, A. J. Meso (tetraphenylporphianato)manganese Ⅲ tetracyanoethenide [Mn~ⅢTPP][TCNE]. A linear chain magnet with a T_c of 18 K. Adv. Mater. 1992, 4, 498-501.
61. Huang, Z. J., Cheng, F., Ren, Y. T., Xue, Y. Y., Chu, C. W., Miller, J. S. Pressure dependence of magnetic ordering temperature for decamethylferrocenium tetracyanoethenide. J. Appl.Phys. 1993, 73, 6563-6565.
62. Miyasaka, H., Madanbashi, T., Sugimoto, K., Nakazawa, Y., Wernsdorfer, W., Sugiura, K.,Yamashita, M., Coulon, C., Cl(?)rac, R. Single-chain magnet behavior in an alternated one-dimensional assembly of a MnⅢ schiff-Base complex and a TCNQ radical. Chem. Eur.J. 2006, 12, 7028 - 7040.
63. Rajsapan, J., Khayrul, K., Gilroy, J. B., Mitchell, K. A. R., Wong, K., Hicks, R. G. High-temperature metal-organic magnets. Nature 2007, 445, 291-284.
64. Pokhodnya, K. I., Bonnet, M., DiPasquale, A. G., Rheingold, A. L., Miller, J. S.Acetonitrile-facilitated reductive dimerization of TCNE to octacyanobutanediide.[C_4(CN)_8]~(2-), by iron(Ⅱ) chloride. Chem. Eur. J. 2008, 14, 714-720.
65. Thorum, M. S., Taliaferro, M. L., Min, K. S., Miller, J. S. The quest for magnets composed of vanadium and 1,4-benzoquinones. Polyhedron 2007, 26, 2247-2251.
66. Min, K. S., DiPasquale, A. G., Golen, J. A., Rheingold, A. L., Miller, J. S. Synthesis,structure, and magnetic properties of valence ambiguous dinuclear antiferromagnetically coupled cobalt and ferromagnetically coupled iron complexes containing the chloranilate(2-) and the significantly stronger coupling chloranilate(·3-) radical trianion. J. Am. Chem. Soc.2007, 129, 2360-2368.
67. Tamaki, H., Mitsumi, M., Nakamura, K., Matsumoto, N., Kida, S., Okawa, H., Iijima, S.Metal-complex ferrimagnets with the formula {NBu_4[M(Ⅱ)Fe(Ⅲ)(ox)_3]}3∞ (NBu_4~+=Tetra(n-butyl)ammonium ion, ox~(2-)= oxalate ion, M=Fe~(2+), Ni~(2+)), Chem. Lett. 1992.250, 1975-1978.
68. Ohba, M., Maruono, N., Okawa, H., Enoki, T., Latour, J. M. A new bimetallic ferromagnet.[Ni(en)_2]_3[Fe(CN)_6]_2·2H_2O, with a rare rope-ladder chain structure, J. Am. Chem. Soc. 1994,116, 11566-11567.
69. Pei, Y., Kahn, O., Sletten, J. Polymetallic systems with subtle spin orders. J. Am. Chem. Soc.1986, 108, 3143-3145.
70. Kahn, O., Pei, Y., Verdaguer, M., Renard, J. P., Sletten, J. Magnetic ordering of manganese(Ⅱ) copper(Ⅱ) bimetallic chains; design of a molecular based ferromagnet. J. Am. Chem. Soc.1988, 110, 782-789.
71. B(?)nard, S., Rivi(?)re, E., Pei, Y., Nakatani, K., Delouis, J. F. A photochromic molecule-based magnet. Chem. Mater. 2001, 13,159-162.
72. Genin, H.; Hoffmann, R. Theoretical tinkering: the search for magnetically ordered organic polymers built from sulfur, carbon, nitrogen-containing five-membered rings.Macromolecules 1998, 31,444-455.
73．孙维林．新型芳杂环高分子材料的探索- 含噻唑环的聚酰亚胺、聚西佛碱的合成及性质研究．中国科学院化学所博士后研究工作报告．1996．
74. Weng, J., Jiang, L. M., Sun, W. L., Shen, Z. Q., Liang, S. Q. Synthesis and magnetic properties of novel complexes of polymer containing bithiazole ring and salicylic acid.Polymer 2001, 42, 5491-5494.
75．林彩萍，孙维林，江黎明，沈之荃．芳杂环聚西佛碱Fe~(2+)配合物的合成及磁性能．高分子学报2003，6，826-830．
76. Sun, W. L., Liu, S., He, B. J., Tang, J. B., Shen, Z. Q. New magnetic phenomena of rare earth polymeric complexes. Phys. Lett. A 2004, 328, 463-466.
77．唐建斌，孙维林，江黎明，沈之荃．聚(2，4-噻唑)的合成及其稀土螯合物的磁性能研究．化学通报2004，1，30-32．
78. Sun, W. L., Jiang, L. M., Weng, J., He, B. J., Shen, Z. Q. Bithiazole based polymer and its ferro complex containing hexacyanoferrate(Ⅲ) group: synthesis and ferromagnetic property.Mater. Chem. Phys. 2003, 78, 676-683.
79. Liu, S., Sun, W. L., He, B. J., Shen, Z. Q. Synthesis and properties of oligomers containing substituted bithiazole rings. Eur. Polym. J. 2004, 40, 2043-2051.
80. Sun, W. L., Jiang, L. M., Weng, J., He, B. J., Cen, D. Q., Shen, Z. Q. A novel bithiazole-tetrathiapentalene polymer and its metal complexes. React. & Funct. Polym. 2003, 55.249-254.
81. Lin, C. P., Sun, W. L., Jiang, L. M., Wang, L. Q., Shen, Z. Q. Bithiazole-containing polymeric complex and PVA composite film: preparation and magnetic properties. J. Appl.Polym. Sci. 2004, 93, 1264-1270.
82. Weng, J., Sun, W. L., Jiang, L. M., Shen, Z. Q. Synthesis and magnetic properties of novel bithiazole-containing polymeric complexes. J. Appl. Polym. Sci. 2001, 81, 1353-1359.
83. Zheng, P., Jiang, L. M., Sun, W. L., Shen, Z. Q. Synthesis and magnetic properties of novel poly(N-2-thiazolyl(meth)acrylamide)-Fe(Ⅱ) complexes. J. Appl. Polym. Sci. 2005, 98,83-87.
84. Tang, J. B., Jiang, L. M., Sun, W. L., Shen, Z. Q. Synthesis of poly(thiazole-2,4-diyl)-rare-earth complexes and their magnetic properties. React. & Funct. Polym. 2004, 61,405-410.
85. Jiang, L. M., Sun, W. L., Weng, J., Shen, Z. Q. A novel bithiazole oligomer containing C_(60) and its ferro-complexes: synthesis and magnetic properties. Polymer 2002, 43, 1563-1566.
86. Sun, W. L., Weng, J., Jiang, L. M., Shen, Z. Q. Study on syntheses and magnetic properties of novel bithiazole-containing polymeric complexes. Synth. Met. 2003, 137, 1341-1343.
87. Liu, S., Sun, W. L., Liu, Z. C., Shen, Z. Q. Synthesis and magnetic properties of polymeric complexes containing substituted bithiazole rings. Mater. Chem. Phys. 2004, 86,307-310.
88. He, B. J., Sun, W. L., Wang, M., Liu, S., Shen, Z. Q. Preparation and characterization of a series of novel complexes by single-walled carbon nanotubes (SWNTs) connected poly(amic acid) containing bithiazole ring. Mater. Chem. Phys. 2004, 84, 140-145.
89. He, B. J., Sun, W. L., Wang, M., Shen, Z. Q. Synthesis and magnetic property of a novel SWNT-poly(Schiff base)-Nd~(3+) complex. Mater. Chem. Phys. 2004, 87, 222-226.
90. Zhou, Z. X., Sun, W. L., Yang, J., Tang, J. B., Shen, Z. Q. Synthesis and properties of novel fully conjugated polymers containing bithiazole rings. Polymer 2005, 46, 9495-9500.
91. Zhou, Z. X., Sun, W. L., Tang. J. B., Shen, Z. Q. Synthesis of novel copolymers containing tri(ethylene oxide) segments and bithiazole rings on the backbone and magnetic properties of their complexes. Polymer 2006, 47, 6280-6284.
92. Yang, J., Sun, W. L., Jiang, H. J., Shen, Z. Q. Synthesis and properties of two novel poly(Schiffbase)s and their rare-earth complexes. Polymer 2005, 46(23), 10478-10483.
93. Yang, J., Sun, W. L., Zhou, Z. X., Shen, Z. Q. Synthesis and properties of polymeric complexes containing bithiazole rings and carbazole units. J. Appl. Polym. Sci. 2006, 101(1),443-446.
94. Zheng, P., Sun, W. L., Shen, Z.Q. Synthesis and magnetic properties of novel complexes of poly(N-2-thiazolylmethacrylamide) with Nd(Ⅲ), Pr(Ⅲ), and Sm(Ⅲ). J. Appl. Polym. Sci.2006, 100(2), 1289-1293.
95. Yang, J., Sun, W. L., Lin, W. H., Shen, Z. Q. Comb-like copolymeric complexes based on thiazole ring and ionic liquid. J. Polym. Sci., Part A: Polym. Chem. 2008, 46, 5123-5132
96. Lehn, J. M. Supramolecular chemistry-scope and perspectives molecules, supermolecules,and molecular devices. Angew. Chem. Int. Ed. Engl. 1988, 27, 89-112.
97. Cram, D. J. The design of molecular hosts, guests, and their complexes (Nobel lecture).Angew. Chem. Int. Ed. Engl. 1988, 27, 1009-1020.
98. Pedersen, C. J. The discovery of crown ethers (Nobel lecture). Angew, Chem. Int. Ed. Engl.1988, 27, 1021-1027.
99. Lehn, J. M. Supramolecular chemistry: concept and perspectives. VCH, Weinheim, 1995.
100. Steed, J. W., Atwood, J. L. Supramolecular chemistry. John Wiley&Sons, Ltd., 2000.
101. Leininger, S., Olenyuk, B., Stang, P., J. Self-assembly of discrete cyclic nanostructures mediated by transition metals. Chem. Rev. 2000, 100 (3), 853-907.
102. Lehn, J. M. Toward self-organization and complex matter. Science 2002, 295, 2400-2403.
103. Ligthart, G. B. W. L., Ohkawa, H., Sijbesma, R. P., Meijer, E. W. Complementary quadruple hydrogen bonding in supramolecular copolymers. J. Am. Chem. Soc. 2005, 127 (3), 810-811.
104. Echavarren, A., Galan, A., Lehn, J. M., Mendoza, J. D. Chiral recognition of aromatic carboxylate anions by an optically active abiotic receptor containing a rigid guanidinium binding subunit. J. Am. Chem. Soc. 1989, 111 (13), 4994-4995.
105. Li, H. B., Rief, ML, Oesterhelt, F., Gaub, H. E., Zhang, X., Shen, J. C. Single-molecule force spectroscopy on polysaccharides by AFM-nanomechanical fingerprint of α-(1,4)-linked polysaccharides. Chem. Phys. Lett. 1999, 305, 197-201.
106. Stockton, W. B., Rubner, M. F. Molecular-level processing of conjugated polymers. 4.Layer-by-layer manipulation of polyaniline via hydrogen-bonding interactions.Macromolecules 1997, 30, 2717-2725.
107. Sukhishvili, S. A., Granick, S. Layered, erasable, ultrathin polymer films, J. Am. Chem.Soc. 2000,122,9550-9551.
108. Major, J. S., Blanchard, G. J. Covalently bound polymer multilayers for efficient metal ion sorption.Langmuir 2001, 17, 1163-1168.
109. Such, G. K., Quinn, J. F., Quinn, A., Tjipto, E., Caruso, F. Assembly of ultrathin polymer multilayer films by click chemistry. J. Am. Chem. Soc. 2006, 128, 9318-9319.
110. Kang, E. H., Jin, P. C, Yang, Y. Q., Sun, J. Q., Shen, J. C. A facile room temperature layer-by-layer deposition process for the fabrication of ultrathin films with noncentrosymmetrically oriented azobenzene chromophores. Chem. Commun. 2006,4332-4334.
111. Suzuki, I., Egawa, Y., Mizukawa, Y., Hoshi, T., Anzai, J. Construction of positively-charged layered assemblies assisted by cyclodextrin complexation. Chem. Commun. 2002,164-165
112. Shimazaki, Y., Nakamura, R., Ito, S., Yamamoto, M. Molecular weight dependence of alternate adsorption through charge-transfer interaction. Langmuir 2001, 17, 953-956.
113. Hamada, K., Serizawa, T., Kitayama, T., Fujimoto, N., Hatada, K., Akashi, M. Stepwise stereocomplex assembly of isotactic poly(methyl methacrylate) and syndiotactic poly(alkyl methacrylate)s on surfaces. Langmuir 2001, 17, 5513-5519.
114. Sun, J. Q., Gao, M. Y., Zhu, Feldmann, M. J., M(o|¨)hwald, H. Layer-by-layer depositions of polyelectrolyte/CdTe nanocrystal films controlled by electric fields. J. Mater. Chem. 2002.12, 1775-1778.
115. Shi, L. X., Lu, Y. X., Sun, J. Q., Zhang, J., Sun, C. Q., Liu, J. Q., Shen, J. C. Site-selective lateral multilayer assembly of bienzyme with polyelectrolyte on ITO electrode based on electric field-induced directly layer-by-layer deposition. Biomacromolecules 2003, 4.1161-1167.
116. Ma, N., Zhang, H. Y., Song, B., Wang, Z. Q., Zhang, X. Polymer micelles as building blocks for layer-by-layer assembly: An approach for incorporation and controlled release of water-insoluble dyes. Chem. Mater. 2005, 17, 5065-5069.
117．沈家璁．《超分子层状结构：组装与功能》．科学出版社．2003．
118. Iler, R. K. Multilayers of Collloidal Particles. J. Colloid Interface Sci. 1966, 21,569-594.
119. Decher, G., Hong, J. D. Buildup of ultrathin multilayer films by a self-assembly process. 1.consecutive adsorption of anionic and cationic bipolar amphiphiles and polyelectrolytes on charged surfaces. Makromol. Chem., Macromol. Symp. 1991,46, 321-327.
120. Decher, G., Hong, J. D. Buildup of ultrathin multilayer films by a self-assembly process. 2.consecutive adsorption of anionic and cationic bipolar amphiphiles and polyelectrolytes on charged surfaces. Ber. Bunsen-Ges. Phys. Chem. 1991, 95, 1430-1434.
121. Decher, G. Fuzzy nanoassemblies: Toward layered polymeric multicomposites. Science 1997, 277, 1232-1237.
122. Sun, J. Q., Wang, Z. Q., Wu, L. X., Zhang, X., Shen, J. C., Gao, S., Chi, L. F., Fuchs, H.Investigation of the covalently attached multilayer architecture based on diazo-resins and poly(4-styrene sulfonate). Macromol. Chem. Phys. 2001,202,967-973.
123．李博,曹廷炳．施祖进,曹维孝．顾镇南．功能化单层碳纳米管的自组装．化学学报2001，59，1536-1539．
124. Fou, A. C., Onitsuka, O., Ferreira, M., Rubner, M. F., Hsieh, B. R. Fabrication and properties of light-emitting diodes based on self-assembled multilayers of poly(phenylene vinylene). J. Appl. Phys. 1996, 79, 7501-7509.
125. Zhang, X., Shen, J. C. Self-assembled ultrathin films: from layered nanoarchitectures to functional assemblies. Adv. Mater. 1999, 11, 1139-1143.
126. Kurth, D. G., Osterhout, R. In situ analysis of metallosupramolecular coordination polyelectrolyte films by surface plasmon resonance spectroscopy. Langmuir 1999, 15,4842-4846.
127. Liu, X. K., Zhou, L., Geng, We., Sun, J. Q. Layer-by-layer-assembled multilayer films of polyelectrolyte-stabilized surfactant micelles for the incorporation of noncharged organic dyes. Langmuir 2008, 24(22), 12986-12989.
128. Lee, S. W., Kim, B., Chert, S., Shao-Horn, Y., Hammond, P. T. Layer-by-layer assembly of all carbon nanotube ultrathin films for electrochemical applications. J. Am. Chem. Soc.2009, 131 (2), 671-679.
129. Sugawara, T., Matsushita, M. M., lzuoka, A., Wada, N., Takeda, N., Ishikawa, M. An organic ferromagnet: α-phase crystal of 2-(2',5'-dihydroxyphenyl)-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazolyl-1-oxy-3-oxide (α-HQNN). J. Chem. Soc., Chem. Commun.1994, 14, 1723-1724.
130. Cirujeda, J., Mas, M., Molins, E., Panthou, F. L., Laugier, J., Park, J. G., Paulsen, C., Rey,P., Rovira, C., Veciana, J. Control of the structural dimensionality in hydrogen-bonded self-assemblies of open-shell molecules. Extension of intermolecular ferromagnetic interactions in α-phenyl nitroxide radicals into three dimensions. J. Chem. Soc., Chem.Commun. 1995, 7, 709-710.
131. Aliev, F. G.; Correa-Duarte, M. A.; Mamedov, A.; Ostrander, J. W.; Giersig, M.; Liz-Marz(?)n,L. M.; Kotov, N. A. Layer-by-layer assembly of core-shell magnetite nanoparticles: Effect of silica coating on interparticle interactions and magnetic properties. Adv. Mater. 1999,11, 1006-1010.
132. Lu, C. H., Luo, C. Q., Cao, W. X. Self-assembly of a covalentty attached magnetic film from diazoresin and Fe_3O_4 nanoparticles. J. Mater. Chem. 2003, 13,382-384.
133. Culp, J. T., Park, J. H., Benitez, I. O., Huh, Y. D., Meisel, M. W., Talham, D. R. Sequential assembly of homogeneous magnetic Prussian blue films on templated surfaces. Chem.Mater. 2003, 15 (18), 3431-3436.
132. Wang, L., Sun, J. Q. Poly(allylamine hydrochloride)-dextran microgels functionalized with magnetic and luminescent nanoparticles. J. Mater. Chem. 2008, 18, 4042-4049.
135．陈光，崔崇．新材料概论．第一版．科学出版社．2003．46．
136．雅菁，吴芳，周彩楼．材料概论．第一版．重庆大学出版社．2006，71．
137．欧阳均，沈之荃．稀土催化合成橡胶文集．科学出版社，1980．
138．杨德俊．络合滴定的理论和应用．北京，国防工业出版社，1965．
139．秦胜，陈柳生，史焱，廖琦，金熹高．由聚电解质自组装多层膜制备微孔薄膜．高等学校化学学报2005．26．1183-1185．
140. Rasmussen, J. R., Stedronsky, E. R., Whitesides, G. M. Introduction, modification, and characterization of functional groups on the surface of low-density polyethylene film. J.Am. Chem. Soc. 1977, 99, 4736-4745.
141. Bruening, M. L., Zhou, Y. F., Aguilar, G., Agee, R., Bergbreiter, D. E., Crooks, R. M.Synthesis and characterization of surface-grafted, hyperbranched polymer films containing fluorescent, hydrophobic, ion-binding, bioeompatible, and electroactive groups. Langmuir 1997, 13,770-778.
142. Liu, J. G., Xu, D. J., Sun, W. L., Wu, Z. Y., Xu, Y. Z., Wu, J. Y., Chiang, M. Y. Synthesis and crystal structure of a cadmium(Ⅱ) complex with 2,2'-diamino-4,4'-bis-1,3-thiazole. J.Coord. Chem. 2003, 6, 71-76.
143. Liu, J. G., Xu, D. J., Sun, W. L. 2,2'-Diamino-4,4'-bi-1,3-thiazolium fumarate. Acta Cryst.E 2003, 59, 812-813.
144. Ruggli, P., Herzog, M., Wegmann, J., Dahn, H. (U|¨)ber die addition von benzol an symm.Dibrom-diacetyl(carbonylgruppen und arom. kohlenwasserstoffe, 1. mitt.). Helv. Chim.Acta 1946, 29, 95-101.
145. Erlenmeyer, H., Menzi, K. Stereochemische untersuchungen bei dithiazolylen. Helv. Chim.Acta 1948, 31,2065-2075.
146. Jiang, X. Y., Cheng, S. D., Me, S. Y. Practical manual of infrared spectroscopy, Science and Technology Press, Tianjin, China, 1992, 312.
147. Cotton, F. A., Wilkinson, G. Advanced inorganic chemistry. Wiley, New York, 1988, 488.
148. Brandrup, J. E., Immergut, H. Polymer handbook, John Wiley & Sons, Ltd., New York,1989.
149. Odinokov, S. E., Mashkovshky, A. A., Glazunov, V. P., Iogansen, A. V., Rassadin, B. V.Spectral manifestations of intermolecular and interionic hydrogen bonding in adducts of various acids with pyridine. Spectrochim. Acta, Part A 1976, 32, 1355-1363.
150. Kumar, U., Kato, T., Frechet, J. M. J. Use of intermolecular hydrogen bonding for the induction of liquid crystallinity in the side chain of polysiloxanes. J. Am. Chem. Soc. 1992.114,6630-6639.
151. Antonietti, M., Wenz, E., Bronstein, L., Seregina, M. Synthesis and characterization of noble metal colloids in block copolymer micelles. Adv. Mater. 1995, 7, 1000-1005.
152. Chen, S. L., Liu, M. Z., Jin, S. P.,Chen, Y. Synthesis and swelling properties of pH-sensitive hydrogels based on chitosan and poly(methacrylic acid) semi-interpenetrating polymer network. J. Appl. Polym. Sci. 2005, 98,1720-1726.
153. Hao, E. C, Lian, T. Q. Buildup of polymer/Au nanoparticle multilayer thin films based on hydrogen bonding. Chem. Mater. 2000, 12 (11), 3392-3396
154. Prinz, C, Muller, P., Maaloum, M. Langmuir isotherms of quenched and annealed polyelectrolyte brushes. Langmuir 2000, 16,6636-6640.
155. Yokoyama, H., Mates, T. E., Kramer, E. J. Structure of asymmetric diblock copolymers in thin films. Macromolecules 2000, 33, 1888-1898.
156. Willits, R. K., Saltzman, W. M. Synthetic polymers alter the structure of cervical mucus.Biomaterials 2001, 22, 445-452.
157. Fu, Y., Bai, S. L., Cui, S. X., Qiu, D. L., Wang, Z. Q., Zhang, X. Hydrogen-bonding-directed layer-by-layer multilayer assembly: Reconformation yielding microporous films.Macromolecules 2002, 35, 9451-9458.
158. Lu, J., Nguyen, Q., Zhou, L. Z., Xu, B. H., Ping, Z. H. Study of the role of water in the transport of water and THF through hydrophilic membranes by pervaporation. J. Memb. Sci.2003,226, 135-143.
159. Qin, S. H., Qin, D. Q., Ford, W. T., Herrera, J. E., Resasco, D. E. Grafting of poly(4-vinylpyridine) to single-walled carbon nanotubes and assembly of multilayer films. Macromolecules 2004, 37, 9963-9967.
160. Sangribsub, S., Tangboriboonrat, P., Pith, T., Decher, G. Adsorption ofpolystyrene-poly(4-vinylpyridine) diblock copolymer on the assembled latex film. Eur. Polym. J. 2005, 41,1531-1538.
161. Lit, Y. V. X., Hit, W., Ma, Y., Zhang, L. B., Sun, J. Q., Lu, N., Shen, L. C. Patterning layered polymeric multilayer films by room-temperature nanoimprint lithography.Macromol. Rapid Commun. 2006, 27, 505-510.
162. Li, D. X., He, Q., Cui, Y., Li, J. B. Fabrication of pH-responsive nanocomposites of gold nanoparticles/poly(4-vinylpyridine). Chem. Mater. 2007, 19, 412-417.
163. Seol, Y. G., Nob, H. Y., Lee, S. S., Ahn, J. H., Lee, N. E. Mechanically flexible low-leakage multilayer gate dielectrics for flexible organic thin film transistors. Appl. Phys.Lett. 2008, 93(1), 013305-013307.
164. Karasawa, S., Zhou, G. Y., Morikawa, H., Koga, Noboru. Magnetic properties of tetrakis[4-(r-diazobenzyl)-pyridine]bis(thiocyanato-N)cobalt(Ⅱ) in frozen solution after irradiation. Formation of a single-molecule magnet in frozen solution. J. Am. Chem. Soc..2003, 125 (45), 13676-13677.
165. Miyasaka, H., Nakata, K., Lecren, L., Coulon, C., Nakazawa, Y., Fujisaki, T. Sugiura. K.,Yamashita, M., Clerac, R. Two-dimensional networks based on Mn4 complex linked by dicyanamide anion: from single-molecule magnet to classical magnet behavior. J. Am.Chem. Soc. 2006, 128 (11), 3770-3783.
166. Eriksson, J., (?)berg, O., L(?)ngstr(o|¨)m, B. Synthesis of [(11)~C]/[(13)~C] acrylamides by palladium-mediated carbonylation. Eur. J Org. Chem. 2007, 455-461.
167. Nanasawa, M., Min, Y., Hirai, M. Thermachromism of metallophalein in acrylamide copolymers with pendant pyridine substituents. React. Polym. 1995, 24, 139-143.
168. Xiong, H. M., Cheng, M. H., Zhou, Z., Zhang, X., Shen, J. C. A new approach to the fabrication of a self-organizing film of heterostructured polymer/Cu_2S nanoparticles. Adv:Mater. 1998, 10, 529-532.
169. Pearson, R. G. Hard and Soft Acids and Bases. J. Am. Chem. Soc. 1963, 85, 3533-3539.
170. Paw, W., Eisenberg, R. Synthesis, Characterization, and Spectroscopy of Dipyridocate-cholate Complexes of Platinum. Inorg. Chem. 1997, 36, 2287-2293.