Baal Eduard, Klein Marius, Harms Klaus, Sundermeyer Jörg
Chemistry Department and Materials Sciences Center, Philipps-Universität Marburg, Hans-Meerwein-Straße 4, 35032, Marburg, Germany.
Chemistry. 2021 Sep 1;27(49):12610-12618. doi: 10.1002/chem.202101719. Epub 2021 Jul 22.
The synthesis of 2,9-diaza-1,3,8,10-tetratriflato-dibenzoperylene (DDP 3 a) and corresponding 2,9-dimethyl-1,3,8,10-tetratriflato-dibenzoperylene (DBP 3 b) has been developed at multigram scale via reduction of one of the industrially most important high-performance dyes, perylene-3,4,9,10-tetracarboxylic diimide (PTCDI), and of the corresponding dihydroxy peropyrenequinone precursor. The focus of this paper is on the reactivity pattern of 3 a as key intermediate towards highly functionalized 2,9-diazadibenzopyrelenes (DDPs) obtained via catalytic substitution of four triflate by aryl, heteroaryl, alkynyl, aminyl, and O-phosphanyl substituents. The influence of electron-donating substituents (OSiMe , OPt-Bu , N-piperidinyl), electron-withdrawing (OTf, 3,5-bis-trifluoromethyl-phenyl), and of electron-rich π-conjugated (2-thienyl, 4-tert-butylphenyl, trimethylsilyl-ethynyl) substituents on optoelectronic and structural properties of these functionalized DDPs has been investigated via XRD analyses, UV/Vis, PL spectroscopy, and by electroanalytical CV. These results were correlated to results of DFT and TD-DFT calculations. Thus, functionalized DPPs with easily tunable HOMO and LUMO energies and gap became available via a new and reliable synthetic strategy starting from readily available PTCDI.
通过还原工业上最重要的高性能染料之一苝-3,4,9,10-四羧酸二亚胺（PTCDI）及其相应的二羟基苝醌前体，已实现了多克规模的2,9-二氮杂-1,3,8,10-四三氟甲磺酸二苯并苝（DDP 3 a）和相应的2,9-二甲基-1,3,8,10-四三氟甲磺酸二苯并苝（DBP 3 b）的合成。本文重点研究3 a作为关键中间体对通过芳基、杂芳基、炔基、氨基和O-膦基取代基催化取代四个三氟甲磺酸酯而获得的高度官能化2,9-二氮杂二苯并苝（DDPs）的反应模式。通过XRD分析、UV/Vis、PL光谱以及电分析CV研究了供电子取代基（OSiMe 、OPt-Bu 、N-哌啶基）、吸电子取代基（OTf、3,5-双三氟甲基苯基）以及富电子π共轭取代基（2-噻吩基、4-叔丁基苯基、三甲基甲硅烷基乙炔基）对这些官能化DDPs的光电和结构性质的影响。这些结果与DFT和TD-DFT计算结果相关。因此，通过一种从易得的PTCDI出发的新的可靠合成策略，可获得具有易于调节的HOMO和LUMO能量及能隙的官能化DPPs。
