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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\u2010TAA compounds showed promising crystallization properties. Six new X\u2010ray crystal structures were obtained, but neither gave a high\u2010resolution 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.<\/jats:p>","DOI":"10.1002\/chem.202501795","type":"journal-article","created":{"date-parts":[[2025,8,14]],"date-time":"2025-08-14T07:33:36Z","timestamp":1755156816000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":1,"title":["What Makes a Branched Aromatic Compound a Crystallization Chaperone? 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