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Tuning the Molecular Packing of Self‐Assembled Amphiphilic Pt II Complexes by Varying the Hydrophilic Side‐Chain Length

2020; Wiley; Volume: 27; Issue: 14 Linguagem: Inglês

10.1002/chem.202003445

1521-3765

Lorena Herkert, Philipp Selter, Constantin G. Daniliuc, Nils Bäumer, Jasnamol P. Palakkal, Gustavo Fernández, Michael Ryan Hansen,

Metal-Organic Frameworks: Synthesis and Applications

Abstract Understanding the relationship between molecular design and packing modes constitutes one of the major challenges in self‐assembly and is essential for the preparation of functional materials. Herein, we have achieved high precision control over the supramolecular packing of amphiphilic Pt II complexes by systematic variation of the hydrophilic side‐chain length. A novel approach of general applicability based on complementary X‐ray diffraction and solid‐state NMR spectroscopy has allowed us to establish a clear correlation between molecular features and supramolecular ordering. Systematically increasing the side‐chain length gradually increases the steric demand and reduces the extent of aromatic interactions, thereby inducing a gradual shift in the molecular packing from parallel to a long‐slipped organization. Notably, our findings highlight the necessity of advanced solid‐state NMR techniques to gain structural information for supramolecular systems where single‐crystal growth is not possible. Our work further demonstrates a new molecular design strategy to modulate aromatic interaction strengths and packing arrangements that could be useful for the engineering of functional materials based on Pt II and aromatic molecules.