Hartenfels Jan, Berking Tim, Rebelo Ruben Pereira, Tsimopoulou Katerina, Schiele Stefanie, Stark Leon, Frey Wolfgang, Richert Clemens
Institute of Organic Chemistry, University of Stuttgart, 70569, Stuttgart, Germany.
Chemistry. 2025 Sep 24;31(54):e01795. doi: 10.1002/chem.202501795. Epub 2025 Aug 14.
Some tetraaryladamantane (TAA) octa- and tetraethers have the ability to crystallize into well-ordered lattices without full desolvation. In many cases, the solvates then yield high-resolution X-ray crystal structures of the encapsulated liquids. To shed light on this unusual effect of TAAs as crystallization chaperones, we have synthesized a series of spirobiflourene and porphyrin derivatives with four phenyl arms also found in TAA chaperones. Despite the structural similarity, neither of the non-TAA compounds showed promising crystallization properties. Six new X-ray crystal structures were obtained, but neither gave a high-resolution structure of an encapsulated guest. Quantum chemical computations suggest that conformational changes have low activation barriers for the TAAs, which may help to adapt to the structures of guest molecules in tightly packed arrangements. These findings on supramolecular chemistry in the crystalline state may help to design new chaperones with improved properties.
一些四芳基金刚烷（TAA）八醚和四醚能够在不完全去溶剂化的情况下结晶成有序晶格。在许多情况下，这些溶剂化物随后会产生被包封液体的高分辨率X射线晶体结构。为了阐明TAA作为结晶伴侣的这种不寻常作用，我们合成了一系列在TAA伴侣中也发现的带有四个苯臂的螺二芴和卟啉衍生物。尽管结构相似，但非TAA化合物均未表现出有前景的结晶性能。获得了六个新的X射线晶体结构，但均未给出被包封客体的高分辨率结构。量子化学计算表明，构象变化对TAA具有较低的活化能垒，这可能有助于在紧密堆积排列中适应客体分子的结构。这些关于晶态超分子化学的发现可能有助于设计具有改进性能的新型伴侣。
