Computational Chemistry‐Guided Design of Selective Chemoresponsive Liquid Crystals Using Pyridine and Pyrimidine Functional Groups
Computational Chemistry‐Guided Design of Selective Chemoresponsive Liquid Crystals Using Pyridine and Pyrimidine Functional Groups
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DOI：
10.1002/adfm.201703581
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发表时间：
2018-03
影响因子：
19
通讯作者：
Huaizhe Yu;Tibor Szilvási;Prabin Rai;R. Twieg;M. Mavrikakis;N. Abbott
中科院分区：
文献类型：
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作者：
Huaizhe Yu;Tibor Szilvási;Prabin Rai;R. Twieg;M. Mavrikakis;N. Abbott
报道了具有吡啶或嘧啶基团的化学响应性液晶（LC）的计算化学引导设计，所述吡啶或嘧啶基团结合到金属阳离子官能化的表面，以提供对目标蒸气物质（二甲基甲基膦酸酯（DMMP））而不是非目标物质（水）的改进的选择性响应。通过合成4-（4-戊基-苯基）-吡啶和5-（4-戊基-苯基）-嘧啶并量化LC对DMMP和水的响应来测试针对实验的LC设计。与计算结果一致，含吡啶的LC与金属阳离子官能化表面的结合太强，以至于不能对DMMP或水做出响应，而含嘧啶的LC在没有水干扰的情况下对DMMP做出响应时发生表面驱动的取向转变。计算预测并不强烈依赖于假设的金属离子的配位度，但在其能力有限，预测LC响应时，使用大多数空d轨道的阳离子。总的来说，这项工作确定了一类有前途的新的基于嘧啶的化学响应LC，其表现出对水的耐受性增强，这一结果很重要，因为水是基于LC的化学传感策略中普遍存在且特别具有挑战性的化学物质。这项工作还提供了计算化学方法的变革性效用的进一步证据，以设计在特定化学环境中表现出选择性取向反应的LC材料。
Computational chemistry‐guided designs of chemoresponsive liquid crystals (LCs) with pyridine or pyrimidine groups that bind to metal‐cation‐functionalized surfaces to provide improved selective responses to targeted vapor species (dimethylmethylphosphonate (DMMP)) over nontargeted species (water) are reported. The LC designs against experiments are tested by synthesizing 4‐(4‐pentyl‐phenyl)‐pyridine and 5‐(4‐pentyl‐phenyl)‐pyrimidine and quantifying LC responses to DMMP and water. Consistent with the computations, pyridine‐containing LCs bind to metal‐cation‐functionalized surfaces too strongly to permit a response to either DMMP or water whereas pyrimidine‐containing LCs undergo a surface‐driven orientational transition in response to DMMP without interference from water. The computation predictions are not strongly dependent on assumptions regarding the degree of coordination of the metal ions but are limited in their ability to predict LC responses when using cations with mostly empty d orbitals. Overall, this work identifies a promising new class of chemoresponsive LCs based on pyrimidine that exhibits enhanced tolerance to water, a result that is important because water is a ubiquitous and particularly challenging chemical interferent in chemical sensing strategies based on LCs. The work also provides further evidence of the transformative utility of computational chemistry methods to design LC materials that exhibit selective orientational responses in specific chemical environments.