TY - JOUR AU - Martínez-Benito, C. AU - Bauzá, A. AU - Lago, A.B. AU - Ruiz-Pérez, C. AU - Jiménez, C.A. AU - Torres, M.E. AU - Frontera, A. AU - Pasán, J. T1 - Anion-π Interactions in Hollow Crystals of a Copper(II)-Cyamelurate Coordination Complex LA - eng PY - 2018 SP - 2636 EP - 2644 T2 - Crystal Growth and Design SN - 1528-7505 VL - 18 IS - 4 PB - American Chemical Society AB - A novel cyamelurate-based copper(II) coordination compound has been designed from a computational approach to show anion-π interactions between the s-heptazine core and perchlorate anions; therefore, a complex of formula {[Cu(pmta)]3cyam}(ClO4)3 (1) [pmta = N,N,N′,N′′,N′′-pentamethyl-diethylenetriamine and cyam = cyamelurate ligand] was synthesized. The cationic molecule stabilizes in the solid state with two perchlorate anions one above and the other below the cyamelurate aromatic rings in a polar conformation, crystallizing in the R3c noncentrosymmetric space group with a close cubic packing of the cations. The binding energies were calculated to be ca. -175 kcal/mol for the two species 1:OClO3- and 1:O3ClO-, and the anion-π contribution could also be calculated, being ca. -10 kcal/mol. The dielectric and magnetic properties were analyzed showing a semiconductor behavior in the temperature range studied (300-458 K) and a weak antiferromagnetic interaction among the three Cu(II) ions. The crystals of 1 show a hollowed hexagonal prismatic morphology, with hollow diameters up to 300 μm. A mechanism based on oriented growth, dissolution, and recrystallization of the outer shell was proposed to explain these hollowed structures. DO - 10.1021/ACS.CGD.8B00305 UR - https://portalciencia.ull.es/documentos/5e3c3edc29995246bbf613c1 DP - Dialnet - Portal de la Investigación ER -