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通过卟啉配合物Meso-四(4-羧基苯基)卟啉铜(简称Cu(Ⅱ)-TCPP)中的羧基与γ-氨基丙基三乙氧基硅烷(NH2(CH2)3Si(OC2H5)3,KH550)中的氨基的相互化学作用,成功地把卟啉配合物接枝到KH550中,随着KH550中乙氧基的水解与聚合反应的进行,卟啉铜连接到固体介质中,从而大幅度提高了卟啉在无机固体介质中的掺杂浓度. 将反应产物与γ-(2,3-环氧丙氧基)丙基三甲氧基硅烷(CH2CHCH2O(CH2)3Si(OCH3)3,KH560) 相杂化,形成物化性能良好、连接卟啉的有机-无机复合材料. 用红外光谱表征了Cu(Ⅱ)-TCPP与KH550的化学反应产物,用紫外—可见吸收光谱研究Cu(Ⅱ)-TCPP的分子状态. 应用Z扫描技术研究不同Cu(Ⅱ)-TCPP掺杂浓度的复合材料的非线性光学性质,其三介非线性折射率n2达-1.1161×10-16 m2/W.
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关键词:
- 非线性折射率 /
- 有机-无机复合材料 /
- 接枝 /
- Meso-四(4-羧基苯基)卟啉铜
Copper metalloporphyrin was bonded to 3-aminopropltriethoxysilane (NH2(CH2)3Si(OC2H5)3, KH550) by the chemical reaction between the carboxyl group of Cu(Ⅱ) meso-Tertra(4-carboxyphenyl)porphine (Cu(Ⅱ)-TCPP) and amino-group of KH550. The copper metalloporphyrin was connected to gel network after the hydrolysis and condensation of the product. The reaction product of different concentrations was hybridized with 3-glycidoxypropltrimethoxysilane (CH2OCHCH2O(CH2)3Si(OCH3)3, KH560) with sol-gel processing to form sol-gel inorganic material, which has good physical-chemical and optical properties. The cross-linkage of Cu(Ⅱ)-TCPP and KH550 was estimated and confirmed with FT-IR spectroscopy. The state of metalloporphyrin molecules was investiaged by UV/VIS spectra. It was found that the Cu(Ⅱ)-TCPP exists mainly in the state of monomer. Nonlinear optical properties of samples was studied by Z-scan technique using Ti:Sapphire femto-second laser pluses. The nonlinear refractive index n2 reached -1.1161×10-16 m2/W.-
Keywords:
- nonlinear refractive index /
- organic-inorganic materials /
- cross-linkage /
- Cu(Ⅱ) meso-Tertra(4-carboxyphenyl) porphine (Cu(Ⅱ)-TCPP)
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[1] Chen H X, Yan M, Sun W B 2002 New Chem. Mater. 30 35 (in Chinese) [陈红祥、 严 煤、 孙文博 2002 化工新型材料 30 35]
[2] Blau W, Byrne H, Dennis W M, Kelly J M 1985 Opt.Commun. 56 25
[3] Rao S V, Naga Srinivas N K M, Rao D N, Giribabu L, Maiya B G, Philip R, Kumar G R 2000 Opt. Commun. 182 255
[4] Chen Y M, Wang Y X, Jiang L, Zhang X R, Yang J Y, Li Y L, Song Y L 2009 Acta Phys. Sin. 58 995 (in Chinese) [陈玉明、 王玉晓、 蒋 礼、 张学如、 杨俊义、 李玉良、 宋瑛林 2009 58 995]
[5] Zhang B, Liu Z B, Chen S Q, Zhou W Y, Zang W P, Tian J G, Luo D B, Zhu Z A 2007 Acta Phys. Sin. 56 5252 (in Chinese) [张 冰、 刘智波、 陈树琪、 周文远、 臧维平、 田建国、 罗代兵、 朱志昂 2007 56 5252]
[6] Yang M, Si J H, Wang Y X, Li C F 1995 Acta Phys. Sin. 44 419 (in Chinese) [杨 淼、 司金海、 王玉晓、 李淳飞 1995 44 419]
[7] Dou K, Sun X D, Wang X J, Parkhill R, Guo Y, Knobbe E T 1999 IEEE J. Quantum Electron. 35 1004
[8] Sinha A K, Bihari B, Mandal B K, Chen L 1995 Macromolecules 28 5681
[9] Xia H P, Pu B Y, Zhang Y P, Zhang J L, Fang J H, Wang C K 2000 Chin. Sci. Bull. 45 1225 (in Chinese) [夏海平、 浦炳 寅、 张约品、 章践立、 房江华、 王存宽 2000 科学通报 45 1225] 〖10] Xia H P, Masayuki N 2000 Opt. Mater. 45 93
[10] Dai S X, Xu T F, Nie Q H, Chen Y F, Chen F F, Shen X, Wang X S, Zhang X H 2007 J. Wuhan. Univ. Technol. 29 25 (in Chinese) [戴世勋、 徐铁峰、 聂秋华、 陈燕飞、 陈飞飞、 沈 祥、 王训四、 章向华 2007 武汉理工大学学报 29 25 ]
[11] Mansoor S B, Said A A, Wei T H, Hagan D J, Stryland E W V 1990 IEEE J. Quantum Electron. 26 760
[12] Wan Q, Wang T H, Lin C L 2003 Nanotech. 14 L15
[13] Xiao W N, Li R H, Zeng X R, Zhou D J, Zhou J Y 2000 Acta Phys. Sin. 49 1086 (in Chinese) [肖万能、 李润华、 曾学然、 周达君、 周建英 2000 49 1086]
[14] Kobayashi T, Kurokawa F, Uyeda N, Suito E 1970 Spectrochim. Acta Part A 26 1305
[15] Cho H S, Rhee H, Song J K, Min C K, Takase M, Aratani N, Cho S, Osuka A, Joo T, Kim D 2003 J. Am. Chem. Soc. 125 5850
[16] Nakazaki J, Senshu Y, Segawa H 2005 Poly. 24 2538
[17] Lei H, Huang Z L, Wang H Z 2003 Physics 32 19 (in Chinese) [雷 虹、 黄振立、 汪河洲 2003 物理 32 19]
[18] Gayathri C, Ramalingam A 2007 Spectrochim. Acta Part A 68 578
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