Phthalocyanines are a class of organometallic compounds that have been investigated extensively for emerging applications such as organic photovoltaics, organic light-emitting diodes, and thin-film transistors. For these applications, the understanding of molecular structures and intermolecular interactions is extremely crucial and is one of the most promising pathways for designing a new generation of functional materials. Here, the crystal structures of six axially substituted silicon phthalocyanines (SiPcs) with aryloxy groups are reported. Three bis(methylphenoxy) SiPcs with varying methyl positions and two bis(pyridoxy) derivatives with varying nitrogen positions are compared to the bare bis(phenoxy) SiPc. Quantitative analysis is conducted to describe the impact of the position and nature of the functional group/atom on the orientation of the axial aryloxy subtituents as well as on the aromaticity and planarity of the SiPc macrocycle. Quantitative analysis of changes in intermolecular interactions, in particular, π–π interactions, and visual representation using Hirshfeld surfaces are also presented. In all cases, the axial aryloxy substituent determined the solid-state arrangement except for the bis(4-pyridoxy) SiPc, which is isostructural to bis(phenoxy) SiPc.

中文翻译：

---

轴向芳氧基取代基上甲基和氮的位置决定了硅酞菁的晶体结构

酞菁是一类有机金属化合物，已经针对新兴应用进行了广泛研究，例如有机光伏，有机发光二极管和薄膜晶体管。对于这些应用，对分子结构和分子间相互作用的理解是至关重要的，并且是设计新一代功能材料的最有希望的途径之一。在此，报道了六个具有芳氧基的轴向取代的硅酞菁（SiPcs）的晶体结构。将三个甲基位置不同的双（甲基苯氧基）SiPcs和两个氮原子位置变化的两个双（吡啶氧基）衍生物与裸露的双（苯氧基）SiPc进行比较。进行定量分析以描述官能团/原子的位置和性质对轴向芳氧基取代基的取向以及对SiPc大环的芳香性和平面性的影响。还介绍了分子间相互作用（尤其是π-π相互作用）变化的定量分析，以及使用Hirshfeld表面的视觉表示。在所有情况下，轴向芳氧基取代基都决定了固态排列，除了双（4-吡啶氧基）SiPc与双（苯氧基）SiPc同构。