Zigelstein Rachel, Lough Alan J, Bender Timothy P
Department of Chemical Engineering and Applied Chemistry, University of Toronto, 200 College Street, Toronto, Ontario, M5S 3E5, Canada.
Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario, M5S 3H6, Canada.
Acta Crystallogr C Struct Chem. 2024 Oct 1;80(Pt 10):658-680. doi: 10.1107/S2053229624006934. Epub 2024 Sep 4.
The crystal structures of 16 boron subphthalocyanines (BsubPcs) with structurally diverse axial groups were analyzed and compared to elucidate the impact of the axial group on the intermolecular π-π interactions, axial-group interactions, axial bond length and BsubPc bowl depth. π-π interactions between the isoindole units of adjacent BsubPc molecules most often involve concave-concave packing, whereas axial-group interactions with adjacent BsubPc molecules tend to favour the convex side of the BsubPc bowl. Furthermore, axial groups that contain O and/or F atoms tend to have significant hydrogen-bonding interactions, while axial groups containing arene site(s) can participate in π-π interactions with the BsubPc bowl, both of which can strongly influence the crystal packing. Bulky axial groups did tend to disrupt the π-π interactions and/or axial-group interactions, preventing some of the close packing that is seen in BsubPcs with less bulky axial groups. The atomic radius of the heteroatom bonded to boron directly influences the axial bond length, whereas the axial group has minimal impact on the BsubPc bowl depth. Finally, the crystal growth method did not generally appear to have a significant impact on the solid-state arrangement, with the exception of water occasionally being incorporated into crystal structures when hygroscopic solvents were used. These insights can help with the design and fine-tuning of the solid-state structures of BsubPcs as they continue to be developed as functional materials in organic electronics.
分析并比较了16种具有结构多样轴向基团的硼代亚酞菁（BsubPcs）的晶体结构，以阐明轴向基团对分子间π-π相互作用、轴向基团相互作用、轴向键长和BsubPc碗状深度的影响。相邻BsubPc分子的异吲哚单元之间的π-π相互作用最常涉及凹-凹堆积，而与相邻BsubPc分子的轴向基团相互作用则倾向于有利于BsubPc碗状结构的凸面。此外，含有O和/或F原子的轴向基团往往具有显著的氢键相互作用，而含有芳烃位点的轴向基团可以与BsubPc碗状结构参与π-π相互作用，这两者都能强烈影响晶体堆积。庞大的轴向基团确实倾向于破坏π-π相互作用和/或轴向基团相互作用，阻止了在具有较小轴向基团的BsubPcs中出现的一些紧密堆积。直接与硼键合的杂原子的原子半径直接影响轴向键长，而轴向基团对BsubPc碗状深度的影响最小。最后，除了使用吸湿溶剂时水偶尔会掺入晶体结构外，晶体生长方法通常似乎对固态排列没有显著影响。随着BsubPcs继续作为有机电子学中的功能材料得到发展，这些见解有助于其固态结构的设计和微调。
