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首页> 外文期刊>Chemistry: A European journal >Synthesis, optical properties, and aggregation behavior of a triad system based on perylene and oligo(p-phenylene vinylene) units
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Synthesis, optical properties, and aggregation behavior of a triad system based on perylene and oligo(p-phenylene vinylene) units

机译：基于per和低聚（对亚苯基亚乙烯基）单元的三单元组体系的合成，光学性质和聚集行为

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摘要

A donor-acceptor-donor triad molecule with a perylene bisimide derivative as electron acceptor, and an oligo(p-phenylene vinylene) (OPV) derivative as electron donor was synthesized (OPV-PERY-OPV). The structure of the triad was characterized by ~1H and ~(13)C NMR spectroscopy, size-exclusion chromatography (SEC), and MALDI-TOF spectrometry. Absorbance spectra and CD spectroscopic measurements of the triad molecule indicated the formation of aggregates in solvents such as toluene, chloroform, and tetrachloroethane, whereas it was present in the molecularly dissolved state in THF. The ~1H NMR spectra of the molecule in chloroform had, unexpectedly, four doublet peaks for the perylene protons, instead of the two doublets that is generally seen in N,N'-substituted perylene molecules. To understand the aggregation behavior and the splitting of the signals in the ~1H NMR spectra, a simple model compound was synthesized, in which the OPV units were replaced by pehnylgroups (Ph-PERY-Ph). ~1H NMR spectra in CDCl_3 and tetrachloroethane again had four doublet peaks for the perylene protons, whereas in THF the perylene protons gave only a single peak.NOE and COSY spectroscopy were used to assign the peaks to their corresponding perylene protons. UV/Vis and CD spectroscopic measurements indicated that, similar to the OPV-PERY-OPV triad molecule, the model compound Ph-PERY-Ph was also present in the aggregated form in solvents such as toluene, chlorofrm, and tetrachloroethane, and in the molecularly dissolved state in THF. IR measurements of the model molecule in the first set of solvents indicated carbamate bond (-OCO-NH-)-induced intermolecular hydrogen bonding, whereas in THF, the molecule was mostly present in the free form. CPK models with a dimeric structure, in which two perylene molecules are held together by intermolecular hydrogen bonding with the perylene core shifted slightly with respect to one another, could account for the optical properties and the observation of the four different peaks in the ~1H NMR spectra in polar solvent. Temperature-dependent ~1H NMR spectroscopic, UV/Vis, and CD measurements indicated that the transition from the aggregated to the molecularly dissolved state took place at higher temperatures. The electrochemical studies indicated that OPV-PERY-OPV was both p-and n-dopable, whereas Ph-PERY-Ph was only n-dopable. Cyclic voltammetry measurements of Ph-PERY-Ph in THF had two reduction peaks corresponding to the reduction of the perylene core to the monoanion and dianion, respectively. In dichloromethane, however, an additional reduction peak at lower potential was observed. This new reduction peak might arise from the hydrogen-bonded species.
机译：合成了具有per双酰亚胺衍生物作为电子受体和低聚（对亚苯基亚乙烯基）（OPV）衍生物作为电子供体的供体-受体-三单元体分子（OPV-PERY-OPV）。三联体的结构通过〜1H和〜（13）C NMR光谱，尺寸排阻色谱（SEC）和MALDI-TOF光谱表征。三单元组分子的吸收光谱和CD光谱测量表明在溶剂（例如甲苯，氯仿和四氯乙烷）中形成聚集体，而它以分子溶解状态存在于THF中。出乎意料的是，氯仿中该分子的〜1H NMR光谱具有per质子的四个双峰，而不是N，N'-取代的per分子中通常可见的两个双峰。为了了解〜1H NMR光谱中的聚集行为和信号分裂，合成了一个简单的模型化合物，其中OPV单元被苯基取代（Ph-PERY-Ph）。在CDCl_3和四氯乙烷中的〜1 H NMR谱图再次显示four质子的四个双峰，而在THF中per质子仅给出一个峰。使用NOE和COZY光谱将这些峰分配给其相应的per质子。 UV / Vis和CD光谱测量表明，与OPV-PERY-OPV三元组分子相似，模型化合物Ph-PERY-Ph也以聚集形式存在于甲苯，氯仿和四氯乙烷等溶剂中以及分子在THF中的溶解状态。在第一组溶剂中对模型分子的IR测量表明，氨基甲酸酯键（-OCO-NH-）诱导了分子间氢键，而在THF中，该分子主要以游离形式存在。具有二聚体结构的CPK模型，其中两个per分子通过分子间氢键结合在一起，而core核相互之间略有偏移，可以解释其光学性质，并观察到〜1H NMR中的四个不同峰极性溶剂中的光谱。温度相关的〜1H NMR光谱，UV / Vis和CD测量表明，从聚集态到分子溶解态的转变发生在更高的温度下。电化学研究表明，OPV-PERY-OPV既可以p掺杂也可以n掺杂，而Ph-PERY-Ph只能n掺杂。 THF中Ph-PERY-Ph的循环伏安法测量有两个还原峰，分别对应于the核还原为一价阴离子和二价阴离子。但是，在二氯甲烷中，观察到了另一个在较低电势下的还原峰。这个新的还原峰可能来自氢键物种。

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