Insights into the formation of chiral second sphere coordination complexes with aromatic tris amines: combined single crystal X-ray crystallography and molecular modeling analyses

Control over the formation of non-centrosymmetric chiral materials is highly desirable due to their potential applications in areas such as ferroelectricity, piezo- and pyroelectricity, and second harmonic generation.[1] Unfortunately, the development of a reliable approach to induce the formation of a chiral material from achiral molecules remains a great challenge in the field of molecular chemistry.[2] Furthermore, the understanding of the driving forces behind those aggregations is a prerequisite for the design and construction of chiral molecular arrays. C3-symmetrical tripodal molecules have emerged as attractive organic frameworks for the construction of chiral coordination compounds.[3] In the present contribution we report about a family of isostructural, chiral supramolecular networks obtained in the solid state by exploiting second sphere coordination interactions in the self-assembly of achiral tris amines L1 and L2 with tetrahalometallate and halide ions. Quantum-Mechanical calculations (including the usage of approaches specific for crystalline solid phases) provided important insights into the intramolecular and packing interactions which determine chirality, pointing to a direct effect of the methyl groups of the central benzene ring of the tris amines. [4] References [1] (a) P. A. Maggard, C. L. Stern and K. R. Poeppelmeier, J. Am. Chem. Soc., 2001, 123, 7742–7743; (b) M. Liu, L. Zhang and T. Wang, Chem. Rev., 2015, DOI: 10.1021/ Q5 cr500671p. [2] P. S. Halasyamani and K. R. Poeppelmeyer, Chem. Mater., 1998, 10, 2753–2769. [3] Z. Dai and J. W. Canary, New J. Chem., 2007, 31, 1708–1718. [4] H. Yu, L. Li, J. Gao, J. Tong, W. Zheng, M. Cametti, A. Famulari, S.V. Meille, F. Guo and J. Martí-Rujas Journal Article Dalton Trans., 2015,44, 15960-15965. DOI: 10.1039/C5DT02387D, Paper