卟啉-二芳基乙烯分子的合成及其无损读取性能

doi:10.11944/j.issn.1000-0518.2017.05.160313

摘要/Abstract

摘要：

二噻吩乙烯是一类性能优良的有机光致变色化合物,在信息储存领域具有广阔的应用前景,本文以2-甲基噻吩、苯甲醛和吡咯为原料,经过多步反应合成了1-(2-甲基-3-噻吩基)-2-{2-甲基-5-{4-[4-(10,15,20-三苯基-5-卟啉基)苯基]氨基羰基苯基}-3-噻吩基}环戊烯(DTE-TPP),其结构经核磁共振波谱仪(NMR)、质谱(MS)和傅里叶变换红外光谱仪(FTIR)表征确认,通过紫外-可见光谱研究了化合物的光致变色性能、抗疲劳性,并辅以荧光光谱探究了化合物的无损读取功能。结果表明,该化合物在254和660 nm的光照射下,发生可逆的光致变色反应,重复光照8次后其紫外-可见光谱与初始谱图相比无明显差异,显示出良好的抗疲劳性;当激发光为520 nm时,开、闭环异构体有较高的荧光对比度,有望实现数据的无损读取。

关键词: 卟啉, 二噻吩乙烯, 光致变色, 无损读取

Abstract:

The dithienylethene compounds offer broad application prospects in optical memory media due to their great performance in reversible chemical transition with irradiation of appropriate light. In this paper, a novel 1-(2-methyl-3-thienyl)-2-{2-methyl-5-{4-[4-(10,15,20-triphenyl-5-porphinyl)phenyl]aminocarbonylphenyl}-3-thienyl}cyclopentene(DTE-TPP) was synthesized using 2-methylthiophene, benzaldehyde and pyrrole as starting materials, and its structure was fully characterized by nuclear magnetic resonance spectroscopy(NMR), mass spectrometry(MS) and Fourier transform infrared spectrometer(FTIR). Photochromic properties of the target compound, fatigue resistance and nondestructive readout capability were investigated by UV-Vis spectra and fluorescent emission spectroscopy. The UV-Vis spectra results indicate that DTE-TPP undergoes bistable and reversible photochromic reactions under irradiation, which is repeated at least eight times, at 254 and 660 nm light. The ring-opened form and ring-closed form of DTE-TPP exhibit great contrasts in fluorescence spectra(λ_ex=520 nm) and a nondestructive readout method may be achived.

Key words: porphyrin, dithienylethene, photochromic, nondestructive readout

刘成,胡炳成,余传明,李济婷. 卟啉-二芳基乙烯分子的合成及其无损读取性能[J]. 应用化学, 2017, 34(5): 527-533.

LIU Cheng,HU Bingcheng,YU Chuanming,LI Jiting. Synthesis and Nondestructive Information Processing Properties of Diarylethene-Based Porphyrin Derivative[J]. Chinese Journal of Applied Chemistry, 2017, 34(5): 527-533.

参考文献

[1]	Irie M,Fukaminato T,Sasaki T,et al. Organic Chemistry:A Digital Fluorescent Molecular Photoswitch[J]. Nature,2002,420(6917):759-760.
[2]	Chan J C H,Lam W H,Yam V W W. A Highly Efficient Silole-Containing Dithienylethene with Excellent Ehermal Stability and Fatigue Resistance:A Promising Candidate for Optical Memory Storage Materials[J]. J Am Chem Soc,2014,136(49):16994-16997.
[3]	Zou Y,Yi T,Xiao S,et al. Amphiphilic Diarylethene as a Photoswitchable Probe for Imaging Living Cells[J]. J Am Chem Soc,2008,130(47):15750-15751.
[4]	GONG Tao,FENG Jiachun,WEI Wei,et al. Recent Progress in Diarylethene as a Photoswitching Unit[J]. Prog Chem,2006,18(6):698-706 (in Chinese). 龚涛,冯嘉春,韦伟,等. 二芳基乙烯类化合物用作光开关的最新进展[J]. 化学进展,2006,18(6):698-706.
[5]	Areephong J,Logtenberg H,Browne W R,et al. Symmetric Six-Fold Arrays of Photo- and Electrochromic Dithienylethene Switches[J]. Org Lett,2010,12(9):2132-2135.
[6]	Irie M,Yamaguchi T,Nakazumi H,et al. Radiation-Induced Coloration of Photochromic Dithienylethene Derivatives[J]. Bull Chem Soc Jpn,1999,72(5):1139-1142.
[7]	Osuka A,Daisuke F,Shinmori H,et al. Synthesis and Photoisomerization of Dithienylethene-Bridged Diporphyrin[J]. J Org Chem,2001,66(11):3913-3923.
[8]	Uno K,Niikura H,Morimoto M,et al. In Situ Preparation of Highly Fluorescent Dyes upon Photoirradiation[J]. J Am Chem Soc,2011,133(34):13558-13564.
[9]	Irie M,Fukaminato T,Matsuda K,et al. Photochromism of Diarylethene Molecules and Crystals:Memories, Switches, and Actuators[J]. Chem Rev,2014,114(24):12174-12277.
[10]	Jiang J Y,Wang S,Yuan W F,et al. Highly Fluorescent Contrast for Rewritable Optical Storage Based on Photochromic Bisthienylethene-Bridged Naphthalimide Dimer[J]. Chem Mater,2006,18(2):235-237.
[11]	Norsten T B,Branda N R. Photoregulation of Fluorescence in a Porphyrinic Dithienylethene Photochrome[J]. J Am Chem Soc,2001,123(8):1784-1785.
[12]	Zhang J B,Li C P,Huo T R,et al. Photochemical Reaction of Magnesium Tetraphenylporphyrin with Sulfur Dioxide[J]. Chinese Chem Lett,2010,21(7):787-789.
[13]	Seol M L,Choi S J,Choi J M,et al. Hybrid Porphyrin-Silicon Nanowire Field-Effect Transistor by Opto-Electrical Excitation[J]. ACS Nano,2012,6(9):7885-7892.
[14]	ZHENG Chunmei,WANG Tingting,ZENG Heping,et al. Synthesis and Photochromic Properties of Diarylethene-Based Porphyrin Derivatives and Its Metal Complexes[J]. Chinese J Org Chem,2012,32(4):719-726 (in Chinese). 郑春梅,王婷婷,曾和平,等. 卟啉-二芳基乙烯分子及其金属配合物的合成与光致变色特性[J]. 有机化学,2012,32(4):719-726.
[15]	Kim H J,Jang J H,Choi H,et al. Photoregulated Fluorescence Switching in Axially Coordinated Tin(Ⅳ) Porphyrinic Dithienylethene[J]. Inorg Chem,2008,47(7):2411-2415.
[16]	Straight S D,Andreasson J,Kodis G,et al. Molecular AND and INHIBIT Gates Based on Control of Porphyrin Fluorescence by Photochromes[J]. J Am Chem Soc,2005,127(26):9403-9409.
[17]	Tyler B N,Neil R B. Axially Coordinated Porphyrinic Photechromes for Non-destructive Information Processing[J]. Adv Mater,2001,13(5):347-349.
[18]	Gaware V S,Haakerud M,Monika L K,et al. Tetraphenylporphyrin Tethered Chitosan Based Carriers for Photochemical Transfection[J]. J Med Chem,2013,56(3):807-819.
[19]	Linda N L,Jaap J D,Jan H E,et al. Syntheses of Dithienylcyclopentene Optical Molecular Switches[J]. Eur J Org Chem,2003,(1):155-166.
[20]	Kobatake S,Uchida K,Tsuchida E,et al. Photochromism of Diarylethenes Having Isopropyl Groups at the Reactive Carbons. Thermal Cycloreversion of the Closed-Ring Isomers[J]. Chem Lett,2000,(11):1340-1341.
[21]	XU Haijun,WANG Xiaoge. Advances on Application of Diarylethene Photochromic Derivatives[J]. Chem Reag,2012,34(6):513-518 (in Chinese). 徐海军,王晓格. 二芳基乙烯类光致变色单元应用研究进展[J]. 化学试剂,2012,34(6):513-518.
[22]	Nakagawa T,Hasegawa Y,Kawai T. Nondestructive Luminescence Intensity Readout of a Photochromic Lanthanide(Ⅲ) Complex[J]. Chem Commun,2009,(32):5630-5632.