酞菁晶体结构与荧光性质的压力调控

朱陆尧; 王鹏; 翟春光; 胡阔; 姚明光; 刘冰冰

doi:10.7498/aps.68.20190559

摘要

酞菁是一种重要的有机光电材料, 关于其晶体结构和光电性质间的内在关联尚存争议. 本文利用高压原位拉曼散射光谱及荧光光谱技术对酞菁晶体在高压下的结构转变和光学性质进行了研究. 当压力达到12.0 GPa时, 酞菁分子本身仍保持稳定, 没有发生开环反应. 酞菁晶体结构在压力作用下由α相逐渐转变为χ相, 这一转变在卸压后恢复到初始α相. 酞菁的高压荧光光谱研究表明, 荧光强度随压力增高而衰减, 至3.0 GPa时消失. 高压下酞菁分子间所形成的激基缔合物荧光受抑制, 而常压下α相酞菁中观察不到的酞菁分子荧光在高压下出现, 这可能与酞菁晶体中呈平行排列的分子之间在压力下重叠程度减小有关.

关键词:

酞菁 /
高压 /
荧光

Abstract

Phthalocyanine (Pc) is a kind of important photoelectric material, but a lot of questions remain to be clarified, like the relationship between the structure of Pc and its photoelectric property. High pressure is a powerful tool to study the structure transformation. High pressure study on piezochromic materials, which shows color change under high pressure due to structure changing, serves as an effectively way of studying the relationship between materials’ structure and photoelectric property. In this work Raman spectrum is employed to study the phase change of α phase metal-free Pc (α-H₂Pc) under high pressure, meanwhile the effect of pressure on fluorescence (FL) is also studied to show how the Pc’s structure affects the photoelectric property. The diamond anvil cell is employed to achieve the high pressure condition, by using NaCl as a pressure transmitting medium. And Raman and FL measurements are performed by using a LabRam HR Evolution spectrometer equipped with a 473 nm laser. The Raman spectra of α-H₂Pc show to slightly change during compression to 12.0 GPa. The main Raman peaks remain at highest pressure, including the Raman peak from macrocyclic of Pc molecules, which shows the stability of Pc molecules. Note that an enhancement of Raman peak at 623 cm^–1 can be found with the pressure increasing, which appears only in the Raman spectrum of χ phase metal-free Pc (χ-H₂Pc), showing that α-H₂Pc is converted into χ-H₂Pc under pressure. The curve for Raman frequency as a function of pressure shows that no obvious evidence related to bonding or structure transition can be observed, which means that α-H₂Pc is transformed into χ-H₂Pc gradually. For FL spectrum, only the FL of excimer can be found in α-H₂Pc at atmosphere pressure. When the solid α-H₂Pc is compressed, the FL intensity is found to decrease as pressure increases, and it is quenched at 3.0 GPa. The FL of Pc molecule, which is not found in α-H₂Pc at ambient pressure, appears at 0.7 GPa. As the pressure increases, the FL intensity ratio between Pc molecule and excimer is enhanced. Considering the pressure induced phase transition from α-H₂Pc to χ-H₂Pc gradually, the change in FL spectrum should be due to the structure transformation. It is proved that the degree of overlapping between Pc molecules in α-H₂Pc is larger than that in χ-H₂Pc. We think, the degree of overlapping decreases under high pressure, which hinders the formation of excimer. It makes the excimer emission decrease and the FL of Pc molecules appear under high pressure. Our work can explain the relationship between Pc crystal structure and its fluorescence, reveals the kinetic behavior of macromolecules similar to Pc system under high pressure, and provides a new possibility of designing the photoelectric materials with excellent performances.

Keywords:

作者及机构信息

1.
吉林大学超硬材料国家重点实验室, 长春　130012

2.
吉林大学物理学院, 长春　130012

通信作者: 王鹏, wangpengtrrs@jlu.edu.cn ; 刘冰冰, liubb@jlu.edu.cn

基金项目: 国家自然科学基金(批准号: 51320105007, 11634004, 11474121)资助的课题.

Authors and contacts

1.
State Key Laboratory of Superhard Materials, Jilin University, Changchun 130012, China

2.
College of Physics, Jilin University, Changchun 130012, China

Corresponding author: Wang Peng, wangpengtrrs@jlu.edu.cn ; Liu Bing-Bing, liubb@jlu.edu.cn

Funds: Project supported by the National Natural Science Foundation of China (Grant Nos. 51320105007, 11634004, 11474121).

文章全文 : translate this paragraph

参考文献

[1]	Zugenmaier P, Bluhm T L, Deslandes Y, Orts W J, Hamer G K 1997 J. Mater. Sci. 32 5561 Google Scholar
[2]	Sharma V B, Jain S L, Sain B 2003 Tetrahedron Lett. 44 383 Google Scholar
[3]	Janczak J, Kubiak R 1992 J. Alloys Compd. 190 121 Google Scholar
[4]	Kubiak R, Janczak J 1992 J. Alloys Compd. 190 117 Google Scholar
[5]	Hammond R B, Roberts K J, Docherty R, Edmondson M, Gairns R 1996 J. Chem. Soc. Perkin Trans. 28 1527
[6]	Takano S, Enokida T, Kakuta A, Mori Y 1984 Chem. Lett. 13 2037 Google Scholar
[7]	李战强, 李祥高, 李健, 胡雅琴 2013 有机化学 33 891 Li Z Q, Li G Q, Li J, Hu Y Q 2013 Chin. J. Org. Chem. 33 891
[8]	Menzel E R, Jordan K J 1978 Chem. Phys. 32 223 Google Scholar
[9]	Dong Y J, Xu B, Zhang J B, Tan X, Wang L J, Chen J L, Lv H G, Wen S P, Li B, Ye L, Zou B, Tian W J 2012 Angew. Chem. 124 10940 Google Scholar
[10]	Meng X, Qi G Y, Zhang C, Wang K, Zou B, Ma Y G 2015 Chem. Commun. 51 9320 Google Scholar
[11]	Yuan H S, Wang K, Yang K, Liu B B, Zou B 2014 J. Phys. Chem. Lett. 5 2968 Google Scholar
[12]	郭宏伟, 刘然, 王玲瑞, 崔金星, 宋波, 王凯, 刘冰冰, 邹勃 2017 物理学报 66 030701 Google Scholar Guo H W, Liu R, Wang L R, Cui J X, Song B, Wang K, Liu B B, Zou B 2017 Acta Phys. Sin. 66 030701 Google Scholar
[13]	Grenoble D C, Drickamer H G 1971 J. Chem. Phys. 55 1624 Google Scholar
[14]	Aroca R, Dilella D P, Loutfy R O 1982 J. Phys. Chem. Solids 43 707 Google Scholar
[15]	Zhang X X, Bao M, Pan N, Zhang Y X, Jiang J Z 2004 Chin. J. Chem. 22 325
[16]	Lehrer S S 1997 Methods Enzymol. 278 286 Google Scholar
[17]	Birks J B, Kazzaz A A, King T A 1966 Proc. R. Soc. London Ser. A 291 556 Google Scholar
[18]	Tanaka J 1963 Bull. Chem. Soc. Jpn. 36 1237 Google Scholar
[19]	Chandross E A, Dempster C J 1970 J. Am. Chem. Soc. 92 3586 Google Scholar
[20]	Jones P F, Nicol M 1965 J. Chem. Phys. 43 3759 Google Scholar
[21]	Birks J B 1975 Rep. Prog. Phys. 38 903 Google Scholar

施引文献

图 1 样品的XRD表征.黑色竖线是利用文献[3]中α相酞菁晶体结构计算出的结果

Fig. 1. The XRD pattern of sample under ambient pressure. The black lines are from calculation result of α phase metal-free phthalocyanine (α-H₂Pc)^[3]

下载: 全尺寸图片幻灯片

图 2 样品拉曼光谱测试　(a) 常压与卸压样品的拉曼光谱; (b) 酞菁的高压拉曼光谱; (c) 峰位为623 cm^–1的拉曼峰随着压力升高峰强增强

Fig. 2. The Raman spectra of α-H₂Pc: (a) The Raman spectra of sample at ambient pressure and decompressed from 12.0 GPa; (b) the Raman spectra of α-H₂Pc under high pressure; (c) the Raman peak around 623 cm^–1 under high pressure

下载: 全尺寸图片幻灯片

图 3 样品的拉曼峰位随压力的变化

Fig. 3. The Raman frequency of H₂Pc as functions of pressure.

下载: 全尺寸图片幻灯片

图 4 样品的荧光光谱　(a)样品的常压和卸压荧光光谱; (b) 样品的升压荧光光谱; (c) 样品的荧光中心随压力的变化及其线性拟合, 虚线为线性拟合所得直线的延长线; (d) 样品卸压过程中的荧光光谱; (e) 两个荧光中心的峰强比随压力的变化图

Fig. 4. The fluorescence (FL) spectra of α-H₂Pc: (a) The FL spectra of α-H₂Pc at ambient pressure (black line) and decompressed from 4.0 GPa (red line); (b) the FL spectra of α-H₂Pc under high pressure during compressing; (c) the blue and red dots are the position of P1 and P2 during compressing, the blue and red lines are the linear fitting between the position and pressure, and the dash lines are the extension of the blue and red line; (d) the FL spectra of α-H₂Pc under high pressure during decompressing; (e) the intensity ratio of P1 and P2 under high pressure

下载: 全尺寸图片幻灯片

图 5 α相和χ相酞菁的分子排布和重叠程度示意图　(a) α相酞菁的分子排布; (b) χ相酞菁的分子排布; (c) α相酞菁的分子重叠程度; (d) χ相酞菁的分子重叠程度

Fig. 5. The arrangement and overlapping of PC molecules in α-H₂Pc and χ-H₂Pc:　(a) The arrangement of Pc molecules in α-H₂Pc; (b) the arrangement of Pc molecules in χ-H₂Pc; (c) the overlapping of Pc molecules in α-H₂Pc; (d) the overlapping of Pc molecules in χ-H₂Pc ^[1,3].

下载: 全尺寸图片幻灯片

表 1 酞菁α相^[3]、β相^[1]和χ相^[1]的晶体结构信息

Table 1. Structural parameters of different phases of metal-free phthalocyanine^[1,3].

	α相	β相	χ相
空间群	C2/n	P2₁/n	Pna2₁
晶系	单斜	单斜	正交
a/nm	2.6124(3)	1.4796(6)	2.10(1)
b/nm	0.3801(1)	0.47325(6)	0.491(5)
c/nm	2.3889(3)	1.7357(7)	2.31(1)
α/(°)	90	90	90
β/(°)	94.18(2)	104.32(2)	90
γ/(°)	90	90	90

下载: 导出CSV

[1]	Zugenmaier P, Bluhm T L, Deslandes Y, Orts W J, Hamer G K 1997 J. Mater. Sci. 32 5561 Google Scholar
[2]	Sharma V B, Jain S L, Sain B 2003 Tetrahedron Lett. 44 383 Google Scholar
[3]	Janczak J, Kubiak R 1992 J. Alloys Compd. 190 121 Google Scholar
[4]	Kubiak R, Janczak J 1992 J. Alloys Compd. 190 117 Google Scholar
[5]	Hammond R B, Roberts K J, Docherty R, Edmondson M, Gairns R 1996 J. Chem. Soc. Perkin Trans. 28 1527
[6]	Takano S, Enokida T, Kakuta A, Mori Y 1984 Chem. Lett. 13 2037 Google Scholar
[7]	李战强, 李祥高, 李健, 胡雅琴 2013 有机化学 33 891 Li Z Q, Li G Q, Li J, Hu Y Q 2013 Chin. J. Org. Chem. 33 891
[8]	Menzel E R, Jordan K J 1978 Chem. Phys. 32 223 Google Scholar
[9]	Dong Y J, Xu B, Zhang J B, Tan X, Wang L J, Chen J L, Lv H G, Wen S P, Li B, Ye L, Zou B, Tian W J 2012 Angew. Chem. 124 10940 Google Scholar
[10]	Meng X, Qi G Y, Zhang C, Wang K, Zou B, Ma Y G 2015 Chem. Commun. 51 9320 Google Scholar
[11]	Yuan H S, Wang K, Yang K, Liu B B, Zou B 2014 J. Phys. Chem. Lett. 5 2968 Google Scholar
[12]	郭宏伟, 刘然, 王玲瑞, 崔金星, 宋波, 王凯, 刘冰冰, 邹勃 2017 物理学报 66 030701 Google Scholar Guo H W, Liu R, Wang L R, Cui J X, Song B, Wang K, Liu B B, Zou B 2017 Acta Phys. Sin. 66 030701 Google Scholar
[13]	Grenoble D C, Drickamer H G 1971 J. Chem. Phys. 55 1624 Google Scholar
[14]	Aroca R, Dilella D P, Loutfy R O 1982 J. Phys. Chem. Solids 43 707 Google Scholar
[15]	Zhang X X, Bao M, Pan N, Zhang Y X, Jiang J Z 2004 Chin. J. Chem. 22 325
[16]	Lehrer S S 1997 Methods Enzymol. 278 286 Google Scholar
[17]	Birks J B, Kazzaz A A, King T A 1966 Proc. R. Soc. London Ser. A 291 556 Google Scholar
[18]	Tanaka J 1963 Bull. Chem. Soc. Jpn. 36 1237 Google Scholar
[19]	Chandross E A, Dempster C J 1970 J. Am. Chem. Soc. 92 3586 Google Scholar
[20]	Jones P F, Nicol M 1965 J. Chem. Phys. 43 3759 Google Scholar
[21]	Birks J B 1975 Rep. Prog. Phys. 38 903 Google Scholar

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酞菁晶体结构与荧光性质的压力调控