Microwave-assisted Synthesis of Perylene-3,4-dicarboximides: Highly Photostable Fluorescent Dyes
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1091-AA07-08
Microwave-assisted Synthesis of Perylene-3,4-dicarboximides: Highly Photostable Fluorescent Dyes Brian Guthrie, Zixing Wang, and Jian Li School of Materials and Advanced Photovoltaics Center, Arizona State University, 7700 S River Parkway, Tempe, AZ, 85284 ABSTRACT A new method for synthesis of perylene-3,4-dicarboximides (PDCIs) is reported. Modified from a literature reported synthetic method, microwave assisted heating was used to perform the reaction, which not only shortened the original reaction time, from 18 hours to 30 min, but also increased the corresponding reaction yield. A variety of PDCI derivatives were synthesized in order to correlate the influence of substituents on the reaction outcome. Moreover, the photophysical and electrochemical properties of PDCIs are characterized and reported. INTRODUCTION Perylene dyes, e.g. perylene-3,4,9,10-tetracarboxylic bisimides (PTCBI), are used widely for their applications in biochemistry and medicine, due to their high fluorescence quantum yields and great thermal, chemical, and photochemical stability [1]. Compared to PTCBI, PDCIs have similar optical features with higher resistance to photo-induced reduction [2, 3], and they are easier to be functionalized. This makes them desirable for additional applications [4, 5] such as fluorescence labeling, intermediates for the synthesis of near infra-red dyes [6, 7], and molecular photonic devices [8]. The development of new synthetic methods for PDCI has received significant attention and progressed rapidly over the recent years. A typical synthesis of PDCIs required multiple synthetic steps and used perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) as the starting material.[9] Although the reaction yield is reasonable, between 45-62%, this procedure might not be suitable for some aryl substituted imides, owing to their poor solubility in acid and basic solutions. Langhals et al developed a one-step synthetic method to convert PTCDA to PDCI with a good yield (~50%), requiring high reaction temperature and pressure (15 bar) [10], which leads to high fabrication costs. It is well documented that microwave flash heating can dramatically reduce reaction time from days and hours to minutes or seconds [11]. The aim of this work was to examine the effect of microwave irradiation on the synthesis of PDCIs. EXPERIMENT Solvent and commercially available reagents were used without further purification unless otherwise stated. Column chromatography was carried out using alumina (50-200µm). 1H NMR spectra were recorded on a Varian Gemini 400 MHz spectrometer with TMS as the internal reference. High resolution mass spectra (HRMS) were obtained on a Voyager-DE STR MALDI-TOF Biospectrometry Workstation operating in the positive linear mode. The
UV-visible spectra were recorded on a Cary 5G UV-VIS-NIR spectrophotometer (Varian). Steady-state emission experiments at room temperature were performed on a Jobin Yvon Fluorolog spectrofluorometer. Density functional theory (DFT) calculations were performed using the Spa
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