Porphyrins are valuable constituents in optoelectronic, catalytic, and other applications, yet control of intermolecular π–π stacking is invariably essential to attain the desired properties. Superstructures built onto the porphyrin, often via meso‐aryl groups, can afford facial encumbrance that suppresses π–π stacking, although some molecular designs have provided insufficient facial coverage and many have entailed cumbersome syntheses. In this study, a copper(II) porphyrin bearing four meso substituents, namely, {10,20‐bis[2,6‐bis(octyloxy)phenyl]‐5,15‐dibromoporphinato}copper(II), [Cu(C₆₄H₈₂Br₂N₄O₄)], was prepared by metalation of the corresponding free‐base porphyrin and was characterized by single‐crystal X‐ray diffraction. The crystal structure reveals a dihedral angle of 111.1 (2)° for the plane of the meso‐aryl group relative to the plane of the porphyrin, with both aryl groups tilted in the same direction. Each of the four octyloxy groups exhibits a gauche conformation for the –OCH₂CH₂– unit but is extended with four or five anti (–CH₂CH₂–/H) conformations thereafter, causing each octyl group to span the dimension of the macrocycle. In a global frame of reference where the two Br atoms define the north/south poles and the two aryl groups are at antipodes on the equator, two octyl groups of one aryl unit project over the northern hemisphere (covering pyrroles A and B), whereas those of the other aryl unit project over the southern hemisphere (covering pyrroles C and D). Together, the four octyl groups ensheath the two faces of the porphyrin in a self‐wrapped assembly. The closest approach of the Cu atom to an octyl methylene C atom (position 6) is 3.5817 (18) Å, the mean separations of neighboring porphyrin planes are 8.059 (4) and 4.693 (8) Å along the a and c axes, respectively, and the center‐to‐center distances between the Cu atoms of neighboring porphyrins are 10.2725 (4), 12.2540 (6), and 12.7472 (6) Å along the a, b, and c axes, respectively. The Hirshfeld surface analysis and two‐dimensional (2D) fingerprint plots provide information concerning contact interactions in the supramolecular assembly of the solid crystal.

中文翻译：

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铜（II）卟啉的四重烷基包裹阻碍了大分子环π-π在紧凑的超分子包装中的堆积。

卟啉在光电，催化和其他应用中是有价值的成分，但是控制分子间π-π堆积对于获得所需的性能始终是必不可少的。卟啉的上部结构通常通过内消旋-芳基基团提供，可提供面部抑制作用，从而抑制π-π堆积，尽管某些分子设计提供了不足的面部覆盖范围，并且许多设计需要繁琐的合成过程。在这项研究中，铜（II）卟啉带有四个内消旋取代基，即{10,20-双[2,6-双（辛氧基氧基）苯基] -5,15-二溴卟啉}铜（II），[Cu（C ₆₄ H ₈₂ Br ₂ N ₄ O ₄）]，是通过将相应的游离碱卟啉金属化制备的，并通过单晶X射线衍射进行了表征。晶体结构显示，内消旋芳基相对于卟啉平面的二面角为111.1（2）° ，两个芳基均沿相同方向倾斜。四个辛氧基团的呈现出笨拙的构象为-OCH ₂ CH ₂ -单元但被扩展为四个或五个抗（-CH ₂ CH ₂– / H）构象，然后使每个辛基均跨越大环的尺寸。在两个Br原子定义北极/南极且两个芳基位于赤道对映体的全局参考框架中，一个芳基单元的两个辛基在北半球突出（覆盖吡咯A和B），而在南半球的其他芳基单元的那些（覆盖吡咯C和D）。四个辛基基团一起将卟啉的两个表面包裹在一个自包裹的组件中。Cu原子最接近辛基亚甲基C原子（位置6）为3.5817（18）Å，相邻卟啉平面沿a的平均间距为8.059（4）和4.693（8）Å和Ç轴，分别与相邻的卟啉的铜原子之间的中心到中心的距离是10.2725（4），12.2540（6），和12.7472（6）沿A一，b，和c ^轴，分别。Hirshfeld表面分析和二维（2D）指纹图提供了有关固态晶体超分子组装中接触相互作用的信息。