Benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) (isoBBT) is a new electron-withdrawing building block that can be used to obtain potentially interesting compounds for the synthesis of OLEDs and organic solar cells components. The electronic structure and delocalization in benzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole), 4-bromobenzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole), and 4,8-dibromobenzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) were studied using X-ray diffraction analysis and ab initio calculations by EDDB and GIMIC methods and were compared to the corresponding properties of benzo[1,2-c:4,5-c′]bis[1,2,5]thiadiazole (BBT). Calculations at a high level of theory showed that the electron affinity, which determines electron deficiency, of isoBBT was significantly smaller than that of BBT (1.09 vs. 1.90 eV). Incorporation of bromine atoms improves the electrical deficiency of bromobenzo-bis-thiadiazoles nearly without affecting aromaticity, which increases the reactivity of these compounds in aromatic nucleophilic substitution reactions and, on the other hand, does not reduce the ability to undergo cross-coupling reactions. 4-Bromobenzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole) is an attractive object for the synthesis of monosubstituted isoBBT compounds. The goal to find conditions for the selective substitution of hydrogen or bromine atoms at position 4 in order to obtain compounds containing a (het)aryl group in this position and to use the remaining unsubstituted hydrogen or bromine atoms to obtain unsymmetrically substituted isoBBT derivatives, potentially interesting compounds for organic photovoltaic components, was not set before. Nucleophilic aromatic and cross-coupling reactions, along with palladium-catalyzed C-H direct arylation reactions for 4-bromobenzo[1,2-d:4,5-d′]bis([1,2,3]thiadiazole), were studied and selective conditions for the synthesis of monoarylated derivatives were found. The observed features of the structure and reactivity of isoBBT derivatives may be useful for building organic semiconductor-based devices.

中文翻译：

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苯并[1,2-d:4,5-d']双([1,2,3]噻二唑)及其溴代衍生物：分子结构和反应活性

Benzo[1,2-d:4,5-d']bis([1,2,3]thiadiazole) (isoBBT) 是一种新的吸电子结构单元，可用于获得潜在有趣的化合物，用于合成OLED 和有机太阳能电池组件。苯并[1,2-d:4,5-d']双([1,2,3]噻二唑), 4-溴苯并[1,2-d:4,5-d']的电子结构和离域双（[1,2,3]噻二唑）和 4,8-二溴苯并[1,2-d:4,5-d']双（[1,2,3]噻二唑）使用 X 射线衍射进行了研究通过 EDDB 和 GIMIC 方法进行分析和从头计算，并将其与苯并 [1,2-c:4,5-c'] 双 [1,2,5] 噻二唑 (BBT) 的相应性质进行比较。高水平理论的计算表明，决定电子缺陷的 isoBBT 的电子亲和力明显小于 BBT（1.09 对 1.90 eV）。溴原子的加入改善了溴苯并双噻二唑的电缺陷，几乎不影响芳香性，这增加了这些化合物在芳香族亲核取代反应中的反应性，另一方面，不会降低进行交叉偶联反应的能力。4-Bromobenzo[1,2-d:4,5-d']bis([1,2,3]thiadiazole) 是合成单取代 isoBBT 化合物的一个有吸引力的对象。目标是找到选择性取代 4 位氢或溴原子的条件，以获得在此位置含有（杂）芳基的化合物，并利用剩余未取代的氢或溴原子获得不对称取代的 isoBBT 衍生物，可能有趣的有机光伏组件化合物，以前没有设置。研究了 4-溴苯并[1,2-d:4,5-d']双([1,2,3]噻二唑)的亲核芳族反应和交叉偶联反应，以及钯催化的 CH 直接芳基化反应，并发现了合成单芳基化衍生物的选择性条件。观察到的 isoBBT 衍生物的结构和反应性特征可能有助于构建基于有机半导体的器件。