取代基对咪唑[4,5-f]-1,10-邻菲罗啉Ru(Ⅱ)配合物的温敏性能影响

doi:10.7517/j.issn.1674-0475.2015.06.468

影像科学与光化学 ›› 2015, Vol. 33 ›› Issue (6): 468-478.DOI: 10.7517/j.issn.1674-0475.2015.06.468

取代基对咪唑[4,5-f]-1,10-邻菲罗啉Ru(Ⅱ)配合物的温敏性能影响

高云燕, 王子超, 欧植泽, 句宝龙, 黄干, 冯钊

西北工业大学理学院空间应用物理与化学教育部重点实验室, 陕西西安 710072

收稿日期:2015-07-12 修回日期:2015-09-16 出版日期:2015-11-16 发布日期:2015-11-16
通讯作者: 欧植泽
基金资助:
国家自然科学基金(21073143)和西北工业大学研究生创新种子基金(Z2015152)资助

The Effect of Substituent on the Temperature Sensitive Properties of Imidazo[4,5-f]-1,10-phenanthroline Ruthenium(Ⅱ) Complex

GAO Yunyan, WANG Zichao, OU Zhize, JU Baolong, HUANG Gan, FENG Zhao

Ministry of Education Key Laboratory of Space, Applied Physics and Chemistry, Department of Applied Chemistry, School of Science, Northwestern Polytechnical University, Xi'an 710072, Shaanxi, P. R. China

Received:2015-07-12 Revised:2015-09-16 Online:2015-11-16 Published:2015-11-16

摘要/Abstract

摘要：

合成了3种具有不同取代基的咪唑[4, 5-f]-1,10-邻菲罗啉配体L¹~L³及其Ru(Ⅱ)配合物[Ru(L¹)₃]、[Ru(L²)₃]和[Ru(L³)₃],并进行了表征。这些Ru(Ⅱ)配合物在溶液中具有π→π^*跃迁吸收峰和金属到配体的电荷转移跃迁(MLCT)吸收峰,其发光峰位约为590 nm左右。将Ru(Ⅱ)配合物掺杂到聚甲基丙烯酸甲酯(PMMA)中得到相应的温敏漆。Ru(Ⅱ)配合物在PMMA膜中的吸收峰精细结构消失,且在长波方向663 nm附近有新的发射峰,表明Ru(Ⅱ)配合物在PMMA膜中有聚集。温度升高后,Ru(Ⅱ)配合物在PMMA膜中的发射峰强度逐渐减弱。分别计算了在30~60 ℃和60~90 ℃区间内非辐射活化能E_nr和温度灵敏度S_T。结果表明,具有苯基取代的咪唑[4, 5-f]-1,10-邻菲罗啉配体的[Ru(L¹)₃]配合物,比咪唑[4, 5-f]-1,10-邻菲罗啉Ru(Ⅱ)配合物[Ru(L²)₃]及烷基取代基的咪唑[4, 5-f]-1,10-邻菲罗啉Ru(Ⅱ)配合物[Ru(L³)₃]具有更高的温度灵敏度。

关键词: 温敏漆, Ru(Ⅱ)配合物, 温度灵敏度, 聚甲基丙烯酸甲酯膜

Abstract:

Three imidazo[4,5-f]-1,10-phenanthroline derivatives L¹-L³,with different substitutes, and their Ru(Ⅱ) complexes have been synthesized and characterized. These Ru(Ⅱ) complexes show characteristic π→π^* transition and metal-ligand charge transfer (MLCT) transition absorptions, and emission maximums at 590 nm. The Ru(Ⅱ) complexes have been doped into the Poly(methyl methacrylate) (PMMA) and obtained the temperature sensitive paint. In PMMA film, the fined structure of the absorption spectra of the Ru(Ⅱ) complexes disappeared, and a new emission peak at the longer wavelength (663 nm) appeared, indicating the aggregation of Ru(Ⅱ) complexes. The emission intensity of the Ru(Ⅱ) complexes in PMMA film decreases gradually with increase of the temperature. The activation energy of non-radiative process (E_nr) temperature sensitivity (S_T) of compounds are calculated in the range of 30-60 ℃ and 60-90 ℃, respectively. The results indicate that [Ru(L¹)₃] with phenyl substituted imidazo[4,5-f]-1,10-phenanthroline has relatively higher S_T than [Ru(L²)₃] with imidazo[4,5-f]-1,10-phenanthroline and [Ru(L³)₃] with alkyl substituted imidazo[4,5-f]-1,10-phenanthroline.

Key words: temperature sensitive paints, Ru(Ⅱ) complex, temperature sensitivity, poly(methyl methacrylate) film

高云燕, 王子超, 欧植泽, 句宝龙, 黄干, 冯钊. 取代基对咪唑[4,5-f]-1,10-邻菲罗啉Ru(Ⅱ)配合物的温敏性能影响[J]. 影像科学与光化学, 2015, 33(6): 468-478.

GAO Yunyan, WANG Zichao, OU Zhize, JU Baolong, HUANG Gan, FENG Zhao. The Effect of Substituent on the Temperature Sensitive Properties of Imidazo[4,5-f]-1,10-phenanthroline Ruthenium(Ⅱ) Complex[J]. Imaging Science and Photochemistry, 2015, 33(6): 468-478.

参考文献

[1] Moffat R J. Some experimental methods for heat transfer studies[J]. Experimental Thermal and Fluid Science, 1990, 3(1): 14-32.
[2] Liu T, Sullivan J P. Pressure and Temperature Sensitive Paints[M]. Berlin: Springer, 2004.
[3] Liu T, Campbell B, Sullivan J P. Heat transfermeasurement on a wave rider at Mach 10 using fluorescent paint[J]. Journal of Thermophysics & Heat Transfer, 1994, 9(4): 605-611.
[4] Liu T, Woodiga S. Feasibility of global skin friction diagnostics using temperature sensitive paint[J]. Measurement Science & Technology, 2011, 22(11): 115402-115412.
[5] Costantini M, Fey U, Henne U, Klein C. Nonadiabatic surface effects on transition measurements using temperature-sensitive paints[J]. AIAA Journal, 2015, 53(5): 1172-1187.
[6] Huang C, Li C, Wang H, Liou T. The application of temperature-sensitive paints for surface and fluid temperature measurements in both thermal developing and fully developed regions of a microchannel[J]. Journal of Micromechanics and Microengineering, 2013, 23(3): 37001-37007.
[7] Asai K, Kanda H, Kunimasu T. Boundary-layer transition detection in a cryogenic wind tunnel using luminescent paint[J]. Journal of Aircraft, 1997, 34(1): 34-42.
[8] 程果, 魏长平, 任晓明, 王贺. 新的稀土Eu,Tb(Ⅲ)β-二酮三元配合物的合成与光谱性质[J]. 中国稀土学报, 2012, 30(2):157-162. Cheng G, Wei C P, Ren X X, Wang H. Synthesis and photoluminescence properties of neweuropium,terbium(Ⅲ) ternary complexes based on diketone[J]. Journal of the Chinese Society of Rare Earths, 2012, 30( 2) : 157-162.
[9] Sakaue H, Kuriki T, Miyazaki T. A temperature-cancellation method of pressure-sensitive paint on porous anodic alumina using 1-Pyrenesulfonic acid[J]. Journal of Luminescence, 2012, 132(2): 256-260.
[10] Egami Y, Matsuda Y, Yamaguchi H, Niimi T. Property changes of temperature-sensitive paint immobilized in acry-lic polymer matrices[J]. Sensors and Actuators B, 2014, 195(5): 677-681.
[11] Kose M E, Carroll B F, Schanze K S. Preparation and spectroscopic properties of multiluminophore luminescent oxygen and temperature sensor films[J]. Langmuir, 2005, 21(20): 9121-9129.
[12] Stich M I J, Wolfbeis O. Fluorescence sensing and imaging using pressure-sensitive paints and temperature-sensitive paints[J]. Springer Series on Fluorescence, 2008, 5: 429-461.
[13] Xie Y, Huang H, Yao J, Lin G, Jiang G, Liu Y. DNA-binding, photocleavage, cytotoxicity in vitro, apoptosis and cell cycle arrest studies of symmetric ruthenium(Ⅱ) complexes[J]. European Journal of Medicinal Chemistry, 2013, 63(5): 603-610.
[14] Coe B J. Developing iron and ruthenium complexes for potential nonlinear optical applications[J]. Coordination Chemistry Reviews, 2013, 257(9-10): 1438-1458.
[15] 夏虹, 张成波, 刘晓冬, 阚士董, 马於光, 沈家骢.Ru(bpy)₃²⁺聚电解质光致发光电致发光性质[J]. 发光学报,2004, 25(1): 44-45. Xia H, Zhang C B, Liu X D, Kan S D, Ma Y G, Shen J C. Characteristic of photoluminescence and electroluminescence based on tris(bipyridyl) ruthenium(Ⅱ) doped polyelectrolytes[J]. Chinese Journal of Luminescence, 2004, 25(1): 44-45.
[16] Campbell B, Liu T, Sullivan J P. Temperature sensitive fluorescence paint systems[C]. In: 18th AIAA Aerospace Ground Testing Conference. Colorado: Springs, 1994. AIAA 94-2483.
[17] Paw W, Eisenberg R. Synthesis, characterization, and spectroscopy of dipyridocatecholate complexes of platinum[J]. Inorganic Chemistry, 1997, 36(11): 2287-2293.
[18] Rullens F, Vuillaume P Y, Moussa A, Habib-Jiwan J, Laschewsky A. Ordered polyelectrolyte "multilayers". 7. hybrid films self-assembled from fluorescent and smectogenic poly(diallylammonium) salts and delaminated clay[J]. Chemistry of Materials, 2006, 18(13): 3078-3087.
[19] Wu J, Ye B, Wang L, Ji L, Zhou J, Li R, Zhou Z. Bis(2,29-bipyridine)ruthenium(Ⅱ) complexes with imidazo[4,5-f][1,10]-phenanthroline or 2-phenylimidazo[4,5-f][1,10]phenanthroline[J]. Journal of Chemical Society, Dalton Transactions, 1997, 8: 1395-1401.
[20] Li S, Zhang C, Huang S, Hu F, Yin J, Liu S H. Highly selective colorimetric and fluorescent sensors for the fluoride anion based on imidazo[4,5-f]-1,10-phenanthroline metal-complexes[J]. RSC Advances, 2012, 2(10): 4215-4219.
[21] Liu Y, Duan Z, Zhang H, Jiang X, Han J. Selective bin-ding and inverse fluorescent behavior of magnesium ion by podand possessing plural imidazo[4,5-f]-1,10-phenanthroline groups and its Ru(Ⅱ) complex[J]. Journal of Organic Chemistry, 2005, 70(4): 1450-1455.
[22] 高云燕, 曹璐, 欧植泽, 陈晨, 李嫕, 王雪松. 联吡啶[3,2-a:2',3-c]-7-氮杂-吩嗪铜(Ⅰ)配合物的合成、表征及其与DNA的相互作用[J]. 物理化学学报, 2013, 29(10): 2162-2172. Gao Y Y, Cao L, Ou Z Z, Chen C, Li Y, Wang X S. Synthesis and characterization of a Cu(Ⅰ) complex of dipyrido[3,2-a:2',3-c]-7-aza-phenazine and its interaction with DNA[J]. Acta Physico-Chimica Sinica, 2013, 29(10): 2162-2172.
[23] Feng P, Zhu J, Cheng Z, Zhang Z, Zhu X. Reversible addition-fragmentation chain transfer polymerization of 7-(4-(acryloyloxy)butoxy)coumarin[J]. Polymer, 2007, 48(20): 5859-5866.
[24] Holzer W, Gratz H, Schmitt T, Penzkofer A, Costela A, Garcia-Moreno I, Costela A, Sastre I R, Duarte F J. Photo-physical characterization of rhodamine 6G in a 2-hydroxyethyl-methacrylate methyl-methacrylate copolymer[J]. Chemical Physics, 2000, 256(1): 125-136.
[25] 宋亚娇,孙晶,闫玲玲,朱鹏,于文生,李剑. Eu_0.5La_0.5(TTA)₃/PMMA温敏漆的制备及性能研究[J]. 中国稀土学报, 2013, 31(1): 55-59. Song Y J, Sun J, Yan L L, Zhu P, Yu W S, Li J. Preparation and properties of temperature sensitive paint[J]. Journal of the Chinese Society of Rareearths, 2013, 31(1): 55-59.
[26] Chen Y, Xu W, Kou J, Yu B, Wei X, Chao H, Ji L. Aggregation-induced emission of ruthenium(Ⅱ) polypyridyl complex[Ru(bpy)₂(pzta)]²⁺[J]. Inorganic Chemistry Communications, 2010, 13(10): 1140-1143.
[27] Jagassar P S, Perri A, Ibarrola G, Gafney H D. Ligand initiated self-assembly of Pt and Ir nanoparticles about Ru(Ⅱ) diimines in room temperature fluid solution[J]. Journal of Physical Chemistry C, 2013, 117(4): 1925-1934.
[28] Campagna S, Giannetto A, Serroni S, Denti G, Truso S, Mallamace F, Micali N. Aggregation in fluid solution of dendritic supermolecules made of Ruthenium(Ⅱ)- and Osmium(Ⅱ)-polypyridine building blocks[J]. Journal of the American Chemical Society, 1995, 117(6): 1754-1758.
[29] 吴世康. 超分子光化学导论[M]. 北京: 科学出版社,2005. 24-37. Wu S K. An Introduction to Supramolecular Photochemistry[M]. Beijing: Science Press, 2005. 24-37.
[30] 张建成,马金石. 现代光化学[M]. 北京: 化学工业出版社, 2006. 19-46. Zhang J C, Ma J S. Modern Photochemistry[M]. Beijing: Chemical Industry Press, 2006. 20-45.
[31] 宋亚娇, 孙晶, 朱鹏, 闫玲玲, 李剑. 稀土钇掺杂Eu(TTA)₃/PMMA温敏漆的制备及性能分析[J]. 无机化学学报, 2013, 29(6): 1171-1175. Song Y Q, Sun J, Zhu P, Yan L L, Li J. Preparation and properties of rare earth Yttrium doped Eu(TTA)₃/PMMA temperature sensitive paint[J]. Chinese Journal of Inorganic Chemistry, 2013, 29(6): 1171-1175.
[32] Gouin S, Gouterman M. Ideality of pressure-sensitive paint. Ⅱ. effect of annealing on the temperature dependence of the luminescence[J]. Journal of Applied Polymer Science, 2000, 77(13): 2805-2814.
[33] Liu T, Sullivan J P. Heat transfer and flow structures in an excited circular impinging jet[J]. International Journal of Heat & Mass Transfer, 1996, 39(17): 3695-3706.
[34] Guo Z, Zhu W, Xiong Y, Tian H. Multiple logic fluorescent thermometer system based on N-isopropyl methacry-lamide copolymer bearing dicyanomethylene-4H-pyran moiety[J]. Macromolecules, 2009, 42(5): 1448-1453.

取代基对咪唑[4,5-f]-1,10-邻菲罗啉Ru(Ⅱ)配合物的温敏性能影响

The Effect of Substituent on the Temperature Sensitive Properties of Imidazo[4,5-f]-1,10-phenanthroline Ruthenium(Ⅱ) Complex

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