揭示 B-B 键的电子特性：双儿茶酚二硼分子,Physical Chemistry Chemical Physics

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揭示 B-B 键的电子特性：双儿茶酚二硼分子
Physical Chemistry Chemical Physics ( IF 2.9 ) Pub Date : 2021-09-28 , DOI: 10.1039/d1cp03428f
D Toffoli ₁ , C Grazioli ₂ , M Monti ₁ , M Stener ₁ , R Totani ₃ , R Richter ₄ , L Schio ₂ , G Fronzoni ₁ , A Cossaro _{1,

2}

Affiliation

二硼分子的电子特性，即双(儿茶酚)二硼 (2-(1,3,2-benzodioxaborol-2-yl)-1,3,2-benzodioxaborole) (B ₂ Cat ₂)，已经通过比较光发射 (XPS) 和近边缘 X 射线吸收光谱 (NEXAFS) 实验的结果与 DFT 计算的结果进行了研究。B 1s、C 1s 和O 1s K-edges 已针对分离的气相分子和吸附在Au(111) 表面上的分子进行了研究。所考虑的三个边缘的每个边缘的偏振 NEXAFS 光谱的主要特征不受底物存在的显着影响，相对于孤立的分子，这表明分子-金相互作用很弱。此外，吸附 B ₂ Cat ₂的 NEXAFS 光谱中观察到的二色性之间的比较并且在分离分子的 NEXAFS 光谱中证实了在气相吸收光谱中分配的轨道对称性。向 π(B–B) 键合和 π*(B–B) 反键合终态的转变代表了 B ₂ Cat ₂分子化学中最相关的探针。我们表明，他们的理论描述需要处理不同激发态配置之间的弛豫变化，我们通过使用 ΔSCF-DFT (ΔSCF) 计算成功实现了这一点。

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Revealing the electronic properties of the B–B bond: the bis-catecholato diboron molecule

The electronic properties of a diboron molecule, namely bis(catecholato)diboron (2-(1,3,2-benzodioxaborol-2-yl)-1,3,2-benzodioxaborole) (B₂Cat₂), have been studied by comparing the results of photoemission (XPS) and near edge X-ray absorption spectroscopy (NEXAFS) experiments with the outcome of DFT calculations. The B 1s, C 1s and O 1s K-edges have been investigated for both the isolated gas phase molecule and the adsorbed one on the Au(111) surface. The main features of the polarized NEXAFS spectra at each of the three edges considered are not significantly affected by the presence of the substrate, with respect to the isolated molecule, indicating that the molecule–gold interaction is weak. Moreover, the comparison between the observed dichroism in the NEXAFS spectra of the adsorbed B₂Cat₂ and that in the NEXAFS spectra of the isolated molecule has confirmed the orbital symmetry assigned in the gas phase absorption spectra. The transitions to π(B–B) bonding and π*(B–B) anti-bonding final states represent the most relevant probe of the chemistry of the B₂Cat₂ molecule. We show that their theoretical description requires that the treatment of the relaxation changes among different excited state configurations, which we successfully implemented by using ΔSCF-DFT (ΔSCF) calculations.

更新日期：2021-10-13

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