Embedding heteroatoms in buckybowls is an effective approach to alter their electronic structures and physicochemical properties. However, buckybowls with heteroatoms situated at both the peripheral rim and the central core to modulate the properties are quite rare. Herein, we report buckybowls containing sulfur atoms at the rim and nitrogen atoms in the center with tunable properties according to the state of the sulfur atoms. When the sulfur atoms are in the form of electron-donating sulfide, the buckybowl demonstrates weak fluorescence. It shows a low oxidative potential and elevated frontier molecular orbital energy levels due to the increased electron density. The electron-rich heterobuckybowl can be chemically oxidized to generate monocations and dications with gradually planarized structures according to the oxidation state. Moreover, it can assemble with electron-deficient fullerene C₆₀ to form a 1 : 1 complex in toluene solution and a 2 : 1 complex in the crystalline state with strong intermolecular attractive interactions. After the oxidation of the sulfur atom to an electron-withdrawing sulfonyl group, the buckybowl shows the strongest photoluminescence in both solution and solid states in the regime of heterobuckybowls thus far. A decline in frontier molecular orbital energy levels and weak association behavior with fullerene C₆₀ to generate a 1 : 1 complex in toluene solution are also observed due to the reduced electron density.

中文翻译：

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调节包含多个杂原子的巴克杯的性质

将杂原子嵌入巴克杯是改变其电子结构和理化性质的有效方法。但是，在外围边缘和中心核上都带有杂原子以调节其特性的巴克汉斯很少见。在此，我们报道了一种在边缘处含有硫原子，在中心处含有氮原子且具有根据硫原子状态可调节的性质的鼠缸。当硫原子呈给电子硫化物形式时，巴基杯显示弱荧光。由于电子密度的增加，它显示出低的氧化势和升高的前沿分子轨道能级。可以根据氧化态对富含电子的异水槽进行化学氧化，以生成具有逐渐平面化结构的单阳离子和阳离子。此外，₆₀在甲苯溶液中形成1：1络合物，并在结晶状态下形成2：1络合物，具有强烈的分子间吸引力。在将硫原子氧化成吸电子的磺酰基后，迄今为止，在异质buckybowls的状态下，buckybowl在溶液和固态下均显示出最强的光致发光。由于电子密度降低，还观察到前沿分子轨道能级的下降以及与富勒烯C _60的弱缔合行为，从而在甲苯溶液中生成1：1络合物。