Shedding Light on the Vibrational Signatures in Halogen‐Bonded Graphitic Carbon Nitride Building Blocks
Shedding Light on the Vibrational Signatures in Halogen‐Bonded Graphitic Carbon Nitride Building Blocks
复制标题
揭示卤素-粘结石墨碳氮化碳砌块的振动特征
DOI：
10.1002/cphc.202200812
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发表时间：
2023
期刊：
影响因子：
2.9
通讯作者：
Shuford, Kevin L.
中科院分区：
文献类型：
--
作者：
Ellington, Thomas L.;Devore, Daniel P.;Uvin G. De Alwis, W. M.;French, Kirk A.;Shuford, Kevin L.
用计算振动光谱法研究了卤素和氢键对石墨氮化碳单体与含C-X和C-C键的卤素键（XB）供体之间相互作用的相对贡献。选择振动拉伸频率的传统探测器通常会导致断开的结果。为了阐明这一行为，对先前在M06 - 2X/aVDZ-PP理论水平上鉴定的XB供体和复合物进行了局部模式分析。由于低能量和高能量C-X振动之间的耦合，在分析XB复合物性质或检测XB形成时，C → C伸缩被认为是更好的候选者。局部力常数支持这一结论，因为C C值与σ-孔大小的相关性比C-X值好得多。分子间的局部拉伸力常数也进行了评估，并发现，吸引力以外的卤素键起支持作用，在复杂的形成。
The relative contributions of halogen and hydrogen bonding to the interaction between graphitic carbon nitride monomers and halogen bond (XB) donors containing C−X and C≡C bonds were evaluated using computational vibrational spectroscopy. Conventional probes into select vibrational stretching frequencies can often lead to disconnected results. To elucidate this behavior, local mode analyses were performed on the XB donors and complexes identified previously at the M06‐2X/aVDZ‐PP level of theory. Due to coupling between low and high energy C−X vibrations, the C≡C stretch is deemed a better candidate when analyzing XB complex properties or detecting XB formation. The local force constants support this conclusion, as the C≡C values correlate much better with theσ‐hole magnitude than their C−X counterparts. The intermolecular local stretching force constants were also assessed, and it was found that attractive forces other than halogen bonding play a supporting role in complex formation.