Abstract:The structures of three rhodamine derivatives were optimized by means of DFT/B3LYP method, and the data of the structural parameters and thermodynamic parameters of the excited state and ground state of the three rhodamine derivatives and their vibrational spectra and frontier molecular orbital energy level were obtained. On the basis of fully optimized structures of excited state and ground state, their gas absorption and emission spectra were studied by time-dependent density functional theory (TD-DFT), while the effects of their structural features on thermal stability, frontier molecular orbital and spectra properties were fully analyzed. The results indicate that the compound a has the lowest reverse movement degree of terminal amino among these molecules, and in contrast, the compound b was better conjugated and planar, the reverse movement degree of terminal amino improved, the gas absorption and emission spectra were red shifted, and it has the longest maximum emission wavelength and the lowest thermal stability among these molecules. The compound c was best conjugated and planar, its thermal stability and energy of HOMO were the highest, its HOMO-LUMO gap was most narrow, and it has the longest maximum absorption wavelength. It was found that the reverse movement degree of terminal amino of compound c improved compared to b, so its maximum emission wavelength was blue shifted.
Key words:Modified by amino;Rhodamine derivatives;DFT/B3LYP method;Thermodynamic properties;Spectra
雷永林,霍冀川. 母环氨基修饰罗丹明衍生物的结构、热力学性质及其光谱的理论研究 [J]. 光谱学与光谱分析, 2010, 30(05): 1381-1385.
LEI Yong-lin, HUO Ji-chuan. Theoretical Studies on the Structure, Thermodynamics and Spectral Properties of Rhodamine Derivatives Modified by Amino of Central Ring. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2010, 30(05): 1381-1385.
[1] GAO Yong, ZHANG Min, GUO Bin(高 勇, 张 敏, 郭 斌). J. Chin. Chem. Soc.(化学通报),2009, 72: 15. [2] YANG Bing-cheng, GUAN Ya-feng, TAN Feng(杨丙成, 关亚风, 谭 峰). Chem. Process.(化学进展), 2004, 16(6): 871. [3] Okoh M P,Hunter, Jackie L C, et al. Biochemistry, 2006, 45(49): 14764. [4] Cheng F, Agarwal A, Buddharaju K D, et al. Biosens. Bioelectron., 2008, 24(2): 216. [5] MA Wen-sheng, HUANG Guo-xia, LIANG Ai-hui, et al(麻文胜, 黄国霞,梁爱惠, 等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2009, 29(3): 759. [6] LIU Bao-sheng, WANG Yun-ke, ZHANG Yan-qing, et al(刘保生, 王云科, 张彦青,等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2008, 28(1): 153. [7] Lee M H, Kim H J, Yoon S, et al. Org. Lett., 2008, 10(2): 213. [8] Huang W, Wu D Y, Guo D, et al. Journal of Chemical Society, Dalton Trans., 2009, (12): 2081. [9] Wang Z Q, Liao J F, Diwu Z J. Bioorg. Med. Chem. Lett.,2005, 15: 2335. [10] Vladimir B B, Ionka P P, Ivo K G. Dye. Pigments, 2007, 74: 187. [11] Marina T L, Valter S, Edilson V. J. Non-Cryst. Solids, 2007, 353: 2430. [12] YAN Fan-yong, CHEN Li-gong, YAN Xi-long, et al(颜范勇,陈立功,闫喜龙,等). Chem. Process. (化学进展),2006,18(2/3):252. [13] Guminski Y, Grousseaud M, Cugnasse S, et al. Bioorg. Med. Chem. Lett., 2009, 19(9): 2474. [14] Kuznetsova N, Makarov D, Derkacheva V, et al. Journal of Photochem. Photobiol., A-Chemistry, 2008, 200(2-3): 161. [15] Liu J X, Diwu Z J, Haugland R P, et al. WO0212195, 20. [16] Liu J X, Diwu Z J, Haugland R P, et al. Tetrahedron Lett.,2003, 44(23): 4355.