Synthesis and characterization of perfluoroaryl-substituted siloles and thiophenes: A series of electron-deficient blue light emitting materials
Synthesis and characterization of perfluoroaryl-substituted siloles and thiophenes: A series of electron-deficient blue light emitting materials
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DOI：
10.1021/cm060346u
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发表时间：
2006-07-11
影响因子：
8.6
通讯作者：
Tilley, T. Don
中科院分区：
文献类型：
--
作者：
Geramita, Katharine;McBee, Jennifer;Tilley, T. Don
全氟芳基（Arf）衍生的硅杂环戊烯和噻吩通过亲核芳族取代（SNAr）合成，所述SNAr涉及六氟苯、八氟萘和癸氟联苯与适当的三硫代硅杂环戊烯或三硫代噻吩中间体的反应。这些化合物作为电子传输层和/或蓝光发射体是令人感兴趣的，因为它们具有相对低的LUMO能级，同时保持高HOMO-LUMO能隙。硅杂环戊烯和噻吩在2-和5-位被修饰，而联噻吩取代发生在5-和5 '-位。HOMO-LUMO间隙，如通过紫外-可见光谱测定的，范围在2.79和3.56 eV之间，而光致发光发射光谱揭示从396至506 nm的λ（max，ems）值（对应于紫色至蓝色/绿色发射）。稀溶液状态的量子产率变化从0.01至0.10的噻咯化合物和从0.25至0.71的噻吩为基础的化合物。实验测定的LUMO能级（约为1.25）。-2.6至-2.9eV，通过循环伏安法测定）表明这些化合物是电子传输层的良好候选物。用密度泛函理论计算了化合物的电子性质，并对电荷传输和电致发光行为进行了初步评价。
Perfluoroaryl ( Arf)-derivatized siloles and thiophenes have been synthesized via nucleophilic aromatic substitutions ( SNAr) involving reactions of hexafluorobenzene, octafluoronaphthalene, and decafluorobiphenyl with the appropriate dilithiosilole or dilithiothiophene intermediate. These compounds are of interest as electron-transport layers and/or blue light emitters, as they possess relatively low LUMO energy levels while maintaining high HOMO-LUMO gaps. Siloles and thiophene were modified in the 2- and 5-positions, while bithiophene substitution occurred in the 5- and 5'-positions. The HOMO-LUMO gaps, as determined by UV-vis spectroscopy, range between 2.79 and 3.56 eV, while photoluminescence emission spectra reveal lambda(max,ems) values from 396 to 506 nm ( corresponding to violet to blue/green emission). Dilute solution-state quantum yields varied from 0.01 to 0.10 for the silole compounds and from 0.25 to 0.71 for the thiophene-based compounds. The experimentally determined LUMO levels ( ca. -2.6 to -2.9 eV, as determined by cyclic voltammetry) suggest that these compounds are good candidates for electron-transport layers. DFT calculations were used to investigate the electronic properties of the compounds, and a preliminary assessment of charge transport and electroluminescent behavior was made.