Combining Molecular Motion with a 2,6-Diiodo BODIPY to Engineer Highly Anisotropic Thermomechanical Properties in Organic Binary and Ternary Molecular Materials
Combining Molecular Motion with a 2,6-Diiodo BODIPY to Engineer Highly Anisotropic Thermomechanical Properties in Organic Binary and Ternary Molecular Materials
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DOI：
10.1021/acs.cgd.3c01521
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发表时间：
2024-03
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影响因子：
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通讯作者：
Babak Tahmouresilerd;Jinchun Qiu;Gary C. George;Vivian Woh;M. Crawford Andrews;Shiva Moaven;D. Unruh;Kristin M. Hutchins;Anthony F. Cozzolino
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作者：
Babak Tahmouresilerd;Jinchun Qiu;Gary C. George;Vivian Woh;M. Crawford Andrews;Shiva Moaven;D. Unruh;Kristin M. Hutchins;Anthony F. Cozzolino
设计具有三个独特但可预测的热膨胀轴的材料是一项重大挑战。无机材料和混合框架倾向于在高对称空间群中结晶，这必然通过提供各向同性行为来限制这一点。另一方面，分子有机材料倾向于在较低对称性空间群中结晶，从而提供了实现各向异性性质的重要机会。挑战出现在将有机部件自组装成可预测的布置以提供可预测的热膨胀性质中。在这里，我们展示了工程有机固态材料，表现出各向异性的热机械行为的设计策略。提供了一系列多组分固体，其中一种组分的特征在于策略性地用正交氢键和卤素键供体基团修饰的BODPIY核。一系列尺寸匹配的卤素键受体被用作每个固体中的第二组分。通过匹配分子的尺寸与相互作用强度，我们得到了很好的控制各向异性的热膨胀的分子材料。此外，使用形状-尺寸模仿和分子运动的倾向，一个罕见的三元分子系统，这是同构的两个二元固体成功地实现。在这项研究中的二碘官能化的BODIPY核心先前已被用于光催化剂，卤素键合被假设为驱动力;在这里，我们提供了确证的解决方案和固态证据的分子间卤素键合在多组分固体具有2，6-二碘BODIPY。
Designing materials to have three unique but predictable thermal expansion axes represents a major challenge. Inorganic materials and hybrid frameworks tend to crystallize in high-symmetry space groups, which necessarily limits this by affording isotropic behavior. On the other hand, molecular organic materials tend to crystallize in lower-symmetry space groups, offering significant opportunity to achieve anisotropic properties. The challenge arises in self-assembling the organic components into a predictable arrangement to afford predictable thermal expansion properties. Here, we demonstrate a design strategy for engineering organic solid-state materials that exhibit anisotropic thermomechanical behaviors. Presented are a series of multicomponent solids wherein one component features a BODPIY core strategically decorated with orthogonal hydrogen- and halogen-bond donor groups. A series of size-matched halogen-bond acceptors are used as the second component in each solid. By matching the molecular dimensions with the interaction strength, we obtained good control over the anisotropic thermal expansion of the molecular materials. Moreover, using shape-size mimicry and propensity for molecular motion, a rare ternary molecular system that is isostructural to the two binary solids was successfully achieved. The diiodo-functionalized BODIPY core in this study has been previously used in photocatalysts, and halogen bonding was hypothesized as a driving force; here, we provide corroborating solution and solid-state evidence of intermolecular halogen bonding in multicomponent solids featuring a 2,6-diiodo BODIPY.