树枝状共轭化合物的合成及应用
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摘要
本论文简要介绍了树枝状共轭聚合物和金复合纳米粒子的进展和主要应用。利用环戊二烯酮与炔基的Diels-Alder加成反应,成功制备了外缘带活性官能团的树枝状共轭化合物。一方面经化学修饰后得到硫醇作为金纳米粒子的有机保护层,得到尺寸可控、窄分布的树枝化聚苯/金的核壳结构的复合纳米粒子；另一方面经过进一步的反应,得到希夫碱作为铬的荧光探针。详细讨论了各种因素对反应的影响。用核磁共振氢谱和红外光谱对各步骤的产物进行了表征,证实了实际得到产物的结构。用紫外-可见光谱和透射电镜对金复合纳米粒子的形貌进行了表征。用紫外-可见光谱和荧光光谱对荧光探针的性能进行了评价。树枝化聚苯刚硬、能够保持形状、热稳定性和光化学稳定性好,还是发蓝光的材料。以结构规整的树枝化聚苯作为保护有机层制备金纳米粒子,将金纳米粒子限制在固定的空间里,从而有效地避免金纳米颗粒之间的团聚。同时,选择共轭的树枝化聚苯作为荧光探针,可以增强荧光强度,提高敏感性,达到了识别金属离子的目的。
This paper briefly described the progress and main applications of dendritic conjugated polymer and gold nanoparticles. Conjugated polybenzene with active groups was successfully synthesized via Diels-Alder addition reaction between cyclopentadienone and alkynyl compound. On one hand, dendritic polybenzene-gold composite nanoparticles with narrow size distribution were prepared. The size and morphology of the composite nanoparticles were controllable. On the other hand, after further chemical modification of the dendritic polybenzene, fluorescent probe of chromium were synthesized. The impact of various factors on the modification process was discussed in detail.1H-NMR, and FTIR were used to characterize the structure of the designed compounds. TEM was used to characterize the size and morphology of the composite nanoparticles. UV-vis and FL spectroscopies were used to characterize opitical properties of the compound and the composite nanoparticles. The designed rigid polybenzene was photo-stable and thermal-stable, and it was also a blue light-emitting material. With this polybenzen as protective layer, the gold nanoparticles were restricted to a fixed space and agglomeration was effectively avoided. Meanwhile, choosing dendritic polymer as a fluorescent probe, could enhance the fluorescence intensity and increase sensitivity for the purpose of identification of metal ions.
This paper briefly described the progress and main applications of dendritic conjugated polymer and gold nanoparticles. Conjugated polybenzene with active groups was successfully synthesized via Diels-Alder addition reaction between cyclopentadienone and alkynyl compound. On one hand, dendritic polybenzene-gold composite nanoparticles with narrow size distribution were prepared. The size and morphology of the composite nanoparticles were controllable. On the other hand, after further chemical modification of the dendritic polybenzene, fluorescent probe of chromium were synthesized. The impact of various factors on the modification process was discussed in detail.1H-NMR, and FTIR were used to characterize the structure of the designed compounds. TEM was used to characterize the size and morphology of the composite nanoparticles. UV-vis and FL spectroscopies were used to characterize opitical properties of the compound and the composite nanoparticles. The designed rigid polybenzene was photo-stable and thermal-stable, and it was also a blue light-emitting material. With this polybenzen as protective layer, the gold nanoparticles were restricted to a fixed space and agglomeration was effectively avoided. Meanwhile, choosing dendritic polymer as a fluorescent probe, could enhance the fluorescence intensity and increase sensitivity for the purpose of identification of metal ions.
引文
1. Rajesh, S.; Alison, M. F.; Royce, W. M., Gold Nanoparticles:Past, Present, and Future. Langmuir 2009,25, (24),13840-13851.
2. Fendler, J. H., Wiley-VAH:Weinheim 1998.
3. Shirakawa, H.; Louis, E. J.; MacDiarmid, A. G, et al, Synthesis of Electrically Conducting Organic Polymers:Halogen Derivatives of Polyacetylene. J. Chem. Soc. Chem. Commun 1977, 578.
4. Peng, Q.; Peng, J. B.; Cao, Y., et al, Synthesis and Electroluminescent Properties of Copolymers Based on Fluorene and 2,5-Di(2-hexyloxyphenyl)thiazolothiazole. Macromolecules 2005,38,7292-7298.
5. Xin, Y.; Wen, G A.; Huang, W., et al, Hyperbranched Oxadiazole-Containing Polyfluorenes: Toward Stable Blue Light PLEDs. Macromolecules 2005,38,6755-6758.
6. Heeger, A. J., Synthetic Metals 2002,125,23242.
7. Setayesh, S.; Grimsdale, A. C.; Gulnther, L., et al, Polyfluorenes with Polyphenylene Dendron Side Chains:Toward Non-Aggregating, Light-Emitting Polymers. J. Am. Chem. Soc. 2001,123,946-953.
8. Blumstein, A.; Samuelson, L., Highly Conjugated Ionic Polyacetylenes:Thin-Film Processing and Potential Applications. Adv. Mater.1998,10, (2),173-176.
9. Miura, Y.; Matsumoto, M.; Ushitani, Y, Magnetic and Optical Characterization of Poly (ethynylbenzene) with Pendant Nitroxide Radicals. Macromolecules 1993,26,6673-6675.
10. Ye, J.; Grimsdale, A. C.; Zhao, Y, Analyzing the Optical Properties of a Conjugated Polymer by the Multimode Brownian Oscillator Model.J. Phys. Chem.2010,114, (1),504-508.
11. Huang, W. Y.; Gao, W.; Okamoto, Y, et al, Synthesis and Characterization of Poly (alkyl2substituted phenylene Ethynylene) s. Macromolecules 2001,34,1570-1578.
12. Pei, J.; Wang, J. L.; Zhang, W. B., et al Star-Shaped Polycyclic Aromatics Based on Oligothiophene-Functionalized Truxene:Synthesis, Properties, and Facile Emissive Wavelength Tuning. J. Am. Chem. Soc.2003,125,9944-9945.
13. Maya, F.; Chanteau, S. H.; James, M. T., et al, Synthesis of Fluorinated Oligomers toward Physical Vapor Deposition Molecular Electronics Candidates. Chem. Mater.2005,17, 1331-1345.
14. Sun, M. H.; Li, J.; Bo, Z. S., et al Toward High Molecular Weight Triphenylamine-Based Hyperbranched Polymers. Macromolecules 2005,38,2651-2658.
15. Wang, S.; Todd, E. K.; Wang, Z. Y, et al, Near-Infrared Electrochromism in Electroactive Pentacenediquinone-Containing Poly(aryl ether)s. Chem. Mater.2005,17,6388-6394.
16.金绪刚；龚克成,共轭聚合物应用研究新进展.材料导报1995,6,55-58.
17. Toy, L. G.; Nagai, K.; Freeman, B. D., et al, Pure-Gas and Vapor Permeation and Sorption Properties of Poly [12phenyl222[p2(trimethylsilyl) phenyl] acetylene]. Macromolecules 2000, 33,2516-2524.
18. Kosynkin, D. V.; Tour, J. M., et al, Phenylene Ethynylene Diazonium Salts as Potential Self-Assembling Molecular Devices. Org. Lett.,2001,3, (7),993-995.
19. Li, J.; Bo, z. s., "AB2+AB"Approach to Hyperbranched Polymers Used as Polymer Blue Light Emitting Materials. Macromolecules 2004,37,2013-2015.
20.张璐；封伟,树枝状共轭聚合物研究.化学进展2007,19,337-349.
21. Christopher, D.; Simpson, G. M.; Kai, M., et al, Nanosized Molecular Propellers by Cyclodehydrogenation of Polyphenylene Dendrimers. J. Am. Chem. Soc.2004,126,3139-3147.
22. Wiesler, U. M.; Berresheim, A. J.; Mullen, K., et al, Divergent Synthesis of Polyphenylene Dendrimers:The Role of Core and Branching Reagents upon Size and Shape. Macromolecules 2001,34,187-199.
23. Akiba, H. M.; Sasaki, K.; Yamamoto, K., Self-Organization and Phase Behavior of Hydrogen-Bonded Mixtures of End-Functional Polymer with Surfactant. Macromolecules 2004, 37,(3),1152-1155.
24. Qu, J. Q.; Zhang, J. Y.; Dieter, N., et al, Dendronized Perylene Diimide Emitters: Synthesis, Luminescence, and Electron and Energy Transfer Studies. Macromolecules 2004,37, (22),8297-8306.
25. Christophe, E.; Marsitzky, D.; Friend, R. H., Attaching Perylene Dyes to Polyfluorene: Three Simple, Efficient Methods for Facile Color Tuning of Light-Emitting Polymers. J. Am. Chem. Soc.2003,125, (2),437-443.
26. Kim, Y. H.; Webster, O. W., Hyperbranched polyphenylenes. Macromolecules 1992,25, (21),5561-5572.
27. Daniel, M. C.; Astruc, D., Gold Nanoparticles:Assembly, Supramolecular Chemistry, Quantum-Size-Related Properties, and Applications toward Biology, Catalysis, and Nanotechnology. Chem. Rev.2004,104, (1),293-346.
28. Liu, J. F.; Li, Y. D., General synthesis of colloidal rare earth orthovanadate nanocrystals. J. Mater. Chem.2007,17,1797-1803.
29. Burda, C.; Chen, X. b.; Narayanan, R., et al, Chemistry and Properties of Nanocrystals of Different Shapes. Chem. Rev.2005,105,1025-1102.
30.徐云鹏；田志坚；林励吾,贵金属固体催化剂的纳米结构及催化性能.催化学报2004,25,(4),331-338.
31. Li, Z. Q.; Li, W. Y.; Xia, Y N., Facile Synthesis of BranchedAu Nanostructures by Templating Against a Self-Destructive Lattice of Magnetic Fe Nanoparticles. Angew. Chem. Int. Ed.2008,47,9653-9656.
32. Matteson, M. J.; Stober, W.; Luther, H., Kinetics of the Oxidation of Sulfur Dioxide by Aerosols of Manganese Sulfate. Ind. Eng. Chem. Fund.1969,8, (4),677-687.
33. Krein, E. B.; Zeev, A., Proposed Thermal Pathways for Sulfur Transformations in Organic Macromolecules:Laboratory Simulation Experiments. Geochemical Transformations of Sedimentary Sulfur 1995,612, (7),110-137.
34. Li, X. H.; Li, Y. C; Li, Y. F., et al, Self-Assembly of Gold Nanoparticles Prepared with 3,4-Ethylenedioxythiophene as Reductant. J. Phys. Chem. B 2004,108,5192-5199.
35. Tseng, R. J.; Huang, J. X.; Yang, Y, et al, Polyaniline Nanofiber/Gold Nanoparticle Nonvolatile Memory. NanoLett.2005,5, (6),1077-1080.
36. Hasobe, T.; Imahori, H.; Fukuzumi, S., et al, Photovoltaic Cells Using Composite Nanoclusters of Porphyrins and Fullerenes with Gold Nanoparticles. J. Am. Chem. Soc.2005, 127,1216-1228.
37. Hoeben, F. J. M.; Jonkheijm, P.; Schenning, A. P. H. J., et al, About Supramolecular Assemblies of π-Conjugated Systems. Chem. Rev.2005,105,1491-1546.
38. Herrikhuyzen, J. v.; Janssen, R. A. J.; Schenning, A. P. H. J., et al, Fractal-like Self-Assembly of Oligo(p-phenylene vinylene) Capped Gold Nanoparticles. J. Am. Chem. Soc. 2006,128,686-687.
39. Murray, G.; Kenneth, S., Notes. Alkali Metal Complexes of Phenylalanine Derivatives. J. Org. Chem.1959,24, (1),112-113.
40. Ratnakar, S. J.; Woods, M.; Sherry, A. D., et al, Modulation of Water Exchange in Europium(III) DOTA-Tetraamide Complexes via Electronic Substituent Effects. J. Am. Chem. Soc.2008,130,6-7.
41. Xu, X. j.; Chen, S. Y.; Liu, Y Q., et al High-Efficiency Blue Light-Emitting Diodes Based on a Polyphenylphenyl Compound with Strong Electron-Accepting Groups. Adv. Mater.2007,19, 1281-1285.
42.尹守春；徐洪耀；唐本忠,芳基单取代炔合成方法.合成学2004,12,(1),31-37.
43. Gheneim, R.; Catalina, P. B.; Alessandro, G., Diels-Alder Reactions with Novel Polymeric Dienes and Dienophiles:Synthesis of Reversibly Cross-Linked Elastomers. Macromolecules 2002,35, (19),7246-7253.
44. Aversa, M. C.; Barattucci, A.; Giannetto, P., et al, Synthesis and Asymmetric Diels-Alder Reactions of Enantiopure 3-(Alkylsulfinyl)-l-methoxy-1,3-butadienes. J. Org. Chem.1997,62, (13),43764384.
45. Frank, M.; Klans, M., Dendritic and Hyperbranched Polyphenylenes via a simple Diels-Alder Route. Tetrahedron 1997,53, (45),15349-15366.
46. Du, H. F.; Ding, K. L., Enantioselective Catalysis of Hetero Diels-Alder Reaction and Diethylzinc Addition Using a Single Catalyst. Org. Lett.2003,5, (7),1091-1093.
47. Skrabalak, S. E.; Chen, J. Y.; Xia, Y N., et al, Gold Nanocages:Synthesis, Properties, and Applications. Accounts Chemical Research 2008,4, (12),1587-1595.
48. Sonogashira, K.; Fujikura, Y.; Hagihara, N., et al, Syntheses and properties of cis-and trans-dialkynyl complexes of platinum(II). J. Org. Chem.1978,145, (1),101-108.
49. Sonogashira, K.; Tohda, Y.; Hagihara, N., et al, A convenient synthesis of acetylenes: catalytic substitutions of acetylenic hydrogen with bromoalkenes, iodoarenes and bromopyridines. Tetrahedron Lett.1975,16, (50),4467-4470.
50. Debuigne, A.; Poli, R.; Detrembleur, C., et al, Key Role of Metal-Coordination in Cobalt-Mediated Radical Polymerization of Vinyl Acetate. J. Org. Chem.2009,53,131-147.
51. Michihiro, H.; Shingo, S.; Tetsuro, M., et al, Inhibition of the Formation and Decay of Stilbene Core Radical Cations by the Dendron during the Photoinduced Electron Transfer. J. Phys. Chem. B 2005,109, (2),973-976.
52. Becker, K.; Lupton, J. M.; Mullen, K., Efficient Intramolecular Energy Transfer in Single Endcapped Conjugated Polymer Molecules in the Absence of Appreciable Spectral Overlap. J. Am. Chem. Soc.2006,128, (3),680-681.
53. Flatt, A. K.; Yao, Y. X.; Tour, J. M., et al, Orthogonally Functionalized Oligomers for Controlled Self-Assembly. J. Org. Chem.2004,69,1752-1755.
2. Fendler, J. H., Wiley-VAH:Weinheim 1998.
3. Shirakawa, H.; Louis, E. J.; MacDiarmid, A. G, et al, Synthesis of Electrically Conducting Organic Polymers:Halogen Derivatives of Polyacetylene. J. Chem. Soc. Chem. Commun 1977, 578.
4. Peng, Q.; Peng, J. B.; Cao, Y., et al, Synthesis and Electroluminescent Properties of Copolymers Based on Fluorene and 2,5-Di(2-hexyloxyphenyl)thiazolothiazole. Macromolecules 2005,38,7292-7298.
5. Xin, Y.; Wen, G A.; Huang, W., et al, Hyperbranched Oxadiazole-Containing Polyfluorenes: Toward Stable Blue Light PLEDs. Macromolecules 2005,38,6755-6758.
6. Heeger, A. J., Synthetic Metals 2002,125,23242.
7. Setayesh, S.; Grimsdale, A. C.; Gulnther, L., et al, Polyfluorenes with Polyphenylene Dendron Side Chains:Toward Non-Aggregating, Light-Emitting Polymers. J. Am. Chem. Soc. 2001,123,946-953.
8. Blumstein, A.; Samuelson, L., Highly Conjugated Ionic Polyacetylenes:Thin-Film Processing and Potential Applications. Adv. Mater.1998,10, (2),173-176.
9. Miura, Y.; Matsumoto, M.; Ushitani, Y, Magnetic and Optical Characterization of Poly (ethynylbenzene) with Pendant Nitroxide Radicals. Macromolecules 1993,26,6673-6675.
10. Ye, J.; Grimsdale, A. C.; Zhao, Y, Analyzing the Optical Properties of a Conjugated Polymer by the Multimode Brownian Oscillator Model.J. Phys. Chem.2010,114, (1),504-508.
11. Huang, W. Y.; Gao, W.; Okamoto, Y, et al, Synthesis and Characterization of Poly (alkyl2substituted phenylene Ethynylene) s. Macromolecules 2001,34,1570-1578.
12. Pei, J.; Wang, J. L.; Zhang, W. B., et al Star-Shaped Polycyclic Aromatics Based on Oligothiophene-Functionalized Truxene:Synthesis, Properties, and Facile Emissive Wavelength Tuning. J. Am. Chem. Soc.2003,125,9944-9945.
13. Maya, F.; Chanteau, S. H.; James, M. T., et al, Synthesis of Fluorinated Oligomers toward Physical Vapor Deposition Molecular Electronics Candidates. Chem. Mater.2005,17, 1331-1345.
14. Sun, M. H.; Li, J.; Bo, Z. S., et al Toward High Molecular Weight Triphenylamine-Based Hyperbranched Polymers. Macromolecules 2005,38,2651-2658.
15. Wang, S.; Todd, E. K.; Wang, Z. Y, et al, Near-Infrared Electrochromism in Electroactive Pentacenediquinone-Containing Poly(aryl ether)s. Chem. Mater.2005,17,6388-6394.
16.金绪刚；龚克成,共轭聚合物应用研究新进展.材料导报1995,6,55-58.
17. Toy, L. G.; Nagai, K.; Freeman, B. D., et al, Pure-Gas and Vapor Permeation and Sorption Properties of Poly [12phenyl222[p2(trimethylsilyl) phenyl] acetylene]. Macromolecules 2000, 33,2516-2524.
18. Kosynkin, D. V.; Tour, J. M., et al, Phenylene Ethynylene Diazonium Salts as Potential Self-Assembling Molecular Devices. Org. Lett.,2001,3, (7),993-995.
19. Li, J.; Bo, z. s., "AB2+AB"Approach to Hyperbranched Polymers Used as Polymer Blue Light Emitting Materials. Macromolecules 2004,37,2013-2015.
20.张璐；封伟,树枝状共轭聚合物研究.化学进展2007,19,337-349.
21. Christopher, D.; Simpson, G. M.; Kai, M., et al, Nanosized Molecular Propellers by Cyclodehydrogenation of Polyphenylene Dendrimers. J. Am. Chem. Soc.2004,126,3139-3147.
22. Wiesler, U. M.; Berresheim, A. J.; Mullen, K., et al, Divergent Synthesis of Polyphenylene Dendrimers:The Role of Core and Branching Reagents upon Size and Shape. Macromolecules 2001,34,187-199.
23. Akiba, H. M.; Sasaki, K.; Yamamoto, K., Self-Organization and Phase Behavior of Hydrogen-Bonded Mixtures of End-Functional Polymer with Surfactant. Macromolecules 2004, 37,(3),1152-1155.
24. Qu, J. Q.; Zhang, J. Y.; Dieter, N., et al, Dendronized Perylene Diimide Emitters: Synthesis, Luminescence, and Electron and Energy Transfer Studies. Macromolecules 2004,37, (22),8297-8306.
25. Christophe, E.; Marsitzky, D.; Friend, R. H., Attaching Perylene Dyes to Polyfluorene: Three Simple, Efficient Methods for Facile Color Tuning of Light-Emitting Polymers. J. Am. Chem. Soc.2003,125, (2),437-443.
26. Kim, Y. H.; Webster, O. W., Hyperbranched polyphenylenes. Macromolecules 1992,25, (21),5561-5572.
27. Daniel, M. C.; Astruc, D., Gold Nanoparticles:Assembly, Supramolecular Chemistry, Quantum-Size-Related Properties, and Applications toward Biology, Catalysis, and Nanotechnology. Chem. Rev.2004,104, (1),293-346.
28. Liu, J. F.; Li, Y. D., General synthesis of colloidal rare earth orthovanadate nanocrystals. J. Mater. Chem.2007,17,1797-1803.
29. Burda, C.; Chen, X. b.; Narayanan, R., et al, Chemistry and Properties of Nanocrystals of Different Shapes. Chem. Rev.2005,105,1025-1102.
30.徐云鹏；田志坚；林励吾,贵金属固体催化剂的纳米结构及催化性能.催化学报2004,25,(4),331-338.
31. Li, Z. Q.; Li, W. Y.; Xia, Y N., Facile Synthesis of BranchedAu Nanostructures by Templating Against a Self-Destructive Lattice of Magnetic Fe Nanoparticles. Angew. Chem. Int. Ed.2008,47,9653-9656.
32. Matteson, M. J.; Stober, W.; Luther, H., Kinetics of the Oxidation of Sulfur Dioxide by Aerosols of Manganese Sulfate. Ind. Eng. Chem. Fund.1969,8, (4),677-687.
33. Krein, E. B.; Zeev, A., Proposed Thermal Pathways for Sulfur Transformations in Organic Macromolecules:Laboratory Simulation Experiments. Geochemical Transformations of Sedimentary Sulfur 1995,612, (7),110-137.
34. Li, X. H.; Li, Y. C; Li, Y. F., et al, Self-Assembly of Gold Nanoparticles Prepared with 3,4-Ethylenedioxythiophene as Reductant. J. Phys. Chem. B 2004,108,5192-5199.
35. Tseng, R. J.; Huang, J. X.; Yang, Y, et al, Polyaniline Nanofiber/Gold Nanoparticle Nonvolatile Memory. NanoLett.2005,5, (6),1077-1080.
36. Hasobe, T.; Imahori, H.; Fukuzumi, S., et al, Photovoltaic Cells Using Composite Nanoclusters of Porphyrins and Fullerenes with Gold Nanoparticles. J. Am. Chem. Soc.2005, 127,1216-1228.
37. Hoeben, F. J. M.; Jonkheijm, P.; Schenning, A. P. H. J., et al, About Supramolecular Assemblies of π-Conjugated Systems. Chem. Rev.2005,105,1491-1546.
38. Herrikhuyzen, J. v.; Janssen, R. A. J.; Schenning, A. P. H. J., et al, Fractal-like Self-Assembly of Oligo(p-phenylene vinylene) Capped Gold Nanoparticles. J. Am. Chem. Soc. 2006,128,686-687.
39. Murray, G.; Kenneth, S., Notes. Alkali Metal Complexes of Phenylalanine Derivatives. J. Org. Chem.1959,24, (1),112-113.
40. Ratnakar, S. J.; Woods, M.; Sherry, A. D., et al, Modulation of Water Exchange in Europium(III) DOTA-Tetraamide Complexes via Electronic Substituent Effects. J. Am. Chem. Soc.2008,130,6-7.
41. Xu, X. j.; Chen, S. Y.; Liu, Y Q., et al High-Efficiency Blue Light-Emitting Diodes Based on a Polyphenylphenyl Compound with Strong Electron-Accepting Groups. Adv. Mater.2007,19, 1281-1285.
42.尹守春；徐洪耀；唐本忠,芳基单取代炔合成方法.合成学2004,12,(1),31-37.
43. Gheneim, R.; Catalina, P. B.; Alessandro, G., Diels-Alder Reactions with Novel Polymeric Dienes and Dienophiles:Synthesis of Reversibly Cross-Linked Elastomers. Macromolecules 2002,35, (19),7246-7253.
44. Aversa, M. C.; Barattucci, A.; Giannetto, P., et al, Synthesis and Asymmetric Diels-Alder Reactions of Enantiopure 3-(Alkylsulfinyl)-l-methoxy-1,3-butadienes. J. Org. Chem.1997,62, (13),43764384.
45. Frank, M.; Klans, M., Dendritic and Hyperbranched Polyphenylenes via a simple Diels-Alder Route. Tetrahedron 1997,53, (45),15349-15366.
46. Du, H. F.; Ding, K. L., Enantioselective Catalysis of Hetero Diels-Alder Reaction and Diethylzinc Addition Using a Single Catalyst. Org. Lett.2003,5, (7),1091-1093.
47. Skrabalak, S. E.; Chen, J. Y.; Xia, Y N., et al, Gold Nanocages:Synthesis, Properties, and Applications. Accounts Chemical Research 2008,4, (12),1587-1595.
48. Sonogashira, K.; Fujikura, Y.; Hagihara, N., et al, Syntheses and properties of cis-and trans-dialkynyl complexes of platinum(II). J. Org. Chem.1978,145, (1),101-108.
49. Sonogashira, K.; Tohda, Y.; Hagihara, N., et al, A convenient synthesis of acetylenes: catalytic substitutions of acetylenic hydrogen with bromoalkenes, iodoarenes and bromopyridines. Tetrahedron Lett.1975,16, (50),4467-4470.
50. Debuigne, A.; Poli, R.; Detrembleur, C., et al, Key Role of Metal-Coordination in Cobalt-Mediated Radical Polymerization of Vinyl Acetate. J. Org. Chem.2009,53,131-147.
51. Michihiro, H.; Shingo, S.; Tetsuro, M., et al, Inhibition of the Formation and Decay of Stilbene Core Radical Cations by the Dendron during the Photoinduced Electron Transfer. J. Phys. Chem. B 2005,109, (2),973-976.
52. Becker, K.; Lupton, J. M.; Mullen, K., Efficient Intramolecular Energy Transfer in Single Endcapped Conjugated Polymer Molecules in the Absence of Appreciable Spectral Overlap. J. Am. Chem. Soc.2006,128, (3),680-681.
53. Flatt, A. K.; Yao, Y. X.; Tour, J. M., et al, Orthogonally Functionalized Oligomers for Controlled Self-Assembly. J. Org. Chem.2004,69,1752-1755.