Evaluating the Role of Molecular Heredity in the Optical and Electronic Properties of Cross-Conjugated Benzo[1,2- d :4,5- d ′]bisoxazoles
Evaluating the Role of Molecular Heredity in the Optical and Electronic Properties of Cross-Conjugated Benzo[1,2- d :4,5- d ′]bisoxazoles
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评估分子遗传在交叉共轭苯并[1,2- d :4,5- d ∀²]双恶唑光学和电子性质中的作用
DOI：
10.1021/acsomega.0c01126
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发表时间：
2020
期刊：
影响因子：
4.1
通讯作者：
Jeffries-EL, Malika
中科院分区：
文献类型：
--
作者：
Wheeler, David L.;Diodati, Alex V.;Tomlinson, Aimée L.;Jeffries-EL, Malika
以遗传学原理为设计思想，合成了8个苯并[1，2-d：4，5-d′]双恶唑（BBO），并研究了其交叉共轭子代遗传了线性亲本的哪些特征。评价了在BBO的2，6-或4，8-位上带有4-叔丁基苯（P）或1，3-双（4-叔丁基苯基）苯（M）的四个线性母体和带有两个等电子芳基取代基的各种组合的四个交叉共轭子体。由于M取代基相对于P取代基的体积较大，因此从理论和实验上探讨了空间位阻沿着BBO轴的影响。利用密度泛函理论（DFT）和含时DFT（TD-DFT）研究了每个分子在溶液和固态下的光学和电子性质，并利用紫外光电子能谱（UPS）、紫外-可见（UV-vis）光谱和光致发光（PL）光谱对其进行了表征。理论和实验结果表明，在不影响H → L跃迁能量的情况下，通过取代基的策略性位置可以选择性地调节最高占据分子轨道（HOMO）和最低未占据分子轨道（LUMO）能级.具体来说，理论结果表明，对于BBO儿童，HOMO和LUMO能级分别从4，8-和2，6-父母遗传。发现每个分子都表现出≤451 nm的发射最大值，使其成为蓝色有机发光二极管（OLED）材料的理想候选者。
A series of eight benzo[1,2-d:4,5-d′]bisoxazole (BBOs) were synthesized using the heredity principle as a design motif, whereby we investigated which characteristics of the linear parents were inherited by their cross-conjugated children. Four linear parents bearing 4-tert-butylbenzene (P) or 1,3-bis(4-tert-butylphenyl)benzene (M) at either the 2,6- or 4,8-position on the BBO and four cross-conjugated children bearing various combinations of the two isoelectronic aryl substituents were evaluated. Due to the bulky nature of theMsubstituent compared to that of thePsubstituent, the influence of steric hindrance along the BBO axes was explored theoretically and experimentally. The optical and electronic properties of each molecule were investigated in the solution and solid state using density functional theory (DFT) and time-dependent DFT (TD-DFT) and characterized using ultraviolet photoelectron spectroscopy (UPS), ultraviolet–visible (UV–vis) spectroscopy, and photoluminescence (PL) spectroscopy. The well-correlated theoretical and experimental results showed that the selective tuning of the highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels was possible through the strategic placement of substituents without impacting the H → L transition energy. Specifically, the theoretical results demonstrated that for the BBO children the HOMO and LUMO energy levels were inherited from the 4,8- and 2,6-parents, respectively. Each molecule was found to exhibit emission maxima ≤451 nm, making them ideal candidates for blue organic light-emitting diode (OLED) materials.