The latest advancements in semiempirical Hamiltonians have inspired new confidence for the supramolecular computational predictivity. The advanced accuracy of newly developed semiempirical methods is offered for computations of what can provide a valuable database of molecular tuning recommendations for the synthesis of new supramolecular materials. In this work the very versatile and impactful porphyrin is employed for examination of the first basic chemical tuning factors that may drive specific aggregation motifs. The 1D motifs are examined as a function of peripheral substituent steric bulk. Subsequently, a 1D-wire versus a 3D-square motif is investigated as a function of the metal–ligand effect. For the first time, an interesting effect of misprediction of semiempirical computations is encountered for a small class of these aggregates and is briefly examined with a conformational search analysis. These findings encourage further in silico work which is greatly required for diminishing the current discovery bottleneck in supramolecular chemistry.

中文翻译：

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分子结构对卟啉聚集基序的影响：计算洞察

半经验哈密顿量的最新进展激发了对超分子计算预测性的新信心。新开发的半经验方法的先进准确性可用于计算可以为新超分子材料的合成提供分子调谐建议的有价值的数据库。在这项工作中，使用非常通用且有影响力的卟啉来检查可能驱动特定聚集基序的第一个基本化学调节因素。作为外围取代基空间体积的函数检查一维基序。随后，研究了 1D 线与 3D 方形图案作为金属配体效应的函数。首次，对于一小部分这些聚集体，会遇到半经验计算错误预测的有趣影响，并通过构象搜索分析进行简要检查。这些发现鼓励进一步的计算机工作，这是减少超分子化学中当前发现瓶颈所必需的。