Computational Study of Ground-State Destabilization Effects and Dipole–Dipole Interaction Energies in Amphidynamic Crystals
Computational Study of Ground-State Destabilization Effects and Dipole–Dipole Interaction Energies in Amphidynamic Crystals
复制标题
两性晶体中基态失稳效应和偶极-偶极相互作用能的计算研究
DOI：
10.1021/acs.joc.3c00465
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发表时间：
2024
期刊：
影响因子：
--
通讯作者：
Garcia-Garibay, Miguel A.
中科院分区：
文献类型：
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作者：
Liepuoniute, Ieva;Shan, Jing-Ran;Houk, K. N.;Garcia-Garibay, Miguel A.
基态去稳定是调节两性晶体中旋转势垒的一种有前景的策略。对安装在柱式桨轮金属有机框架中作为旋转器的极性亚苯基进行密度泛函理论研究，以研究基态不稳定对其旋转动力学的影响。我们发现，随着亚苯基取代基的空间尺寸增加，基态不稳定效应也增加。具体来说，随着取代基尺寸的增加，基态能量发生显着的不稳定，值范围为 2 至 11.7 kcal/mol。对取代基对偶极-偶极相互作用能和旋转势垒影响的评估表明，应该可以设计出偶极-偶极相互作用能与旋转势垒相当的两性晶体。值得注意的是，虽然纯偶极-偶极相互作用能量达到 0.6 至 2.4 kcal/mol 的值，但电子和空间效应的包含可以将偶极取向改变为显着更大的值。我们建议仔细选择不同尺寸的极性取代基可能有助于创建具有可切换集体极化的温度响应材料。
Ground-state destabilization is a promising strategy to modulate rotational barriers in amphidynamic crystals. Density functional theory studies of polar phenylenes installed as rotators in pillared paddle-wheel metal organic frameworks were performed to investigate the effects of ground-state destabilization on their rotational dynamics. We found that as the steric size of phenylene substituents increases, the ground-state destabilization effect is also increased. Specifically, a significant destabilization of the ground-state energy occurred as the size of the substituents increased, with values ranging from 2 to 11.7 kcal/mol. An evaluation of the effects of substituents on dipole–dipole interaction energies and rotational barriers suggests that it should be possible to engineer amphidynamic crystals where the dipole–dipole interaction energy becomes comparable to the rotational barriers. Notably, while pure dipole–dipole interaction energies reached values ranging from 0.6 to 2.4 kcal/mol, the inclusion of electronic and steric effects can alter dipolar orientations to significantly greater values. We propose that careful selection of polar substituents with different sizes may help create temperature-responsive materials with switchable collective polarization.