2026-04-29T12:23:46Zhttps://repisalud.isciii.es/rest/oai/request
oai:repisalud.isciii.es:20.500.12105/229382024-11-28T21:22:38Zcom_20.500.12105_15322com_20.500.12105_2051col_20.500.12105_16967
Repisalud author Dabuleanu, Dragos author Bauza, Antonio author Ortega-Castro, Joaquin author Escudero-Adan, Eduardo C author Ballester, Pablo author Frontera, Antonio 2024-09-13T09:13:37Z 2024-09-13T09:13:37Z 2020-01-02 Dabuleanu D, Bauza A, Ortega-Castro J, Escudero-Adan EC, Ballester P, Frontera A. Synthesis, X-ray Characterization and Density Functional Theory (DFT) Studies of Two Polymorphs of the alpha,alpha,alpha,alpha, Isomer of Tetra-p-Iodophenyl Tetramethyl Calix[4]pyrrole: On the Importance of Halogen Bonds. Molecules. 2020 Jan 2;25(2):285. 10.3390/molecules25020285 1420-3049 Molecules https://hdl.handle.net/20.500.13003/19841 31936802 L630622881 2-s2.0-85077884793 https://hdl.handle.net/20.500.12105/22938 515381800047 This manuscript reports the improved synthesis of the alpha,alpha,alpha,alpha isomer of tetra-p-iodophenyl tetra-methyl calix[4]pyrrole and the X-ray characterization of two solvate polymorphs. In the solid state, the calix[4]pyrrole receptor adopts the cone conformation, including one acetonitrile molecule in its aromatic cavity by establishing four convergent hydrogen bonds between its nitrogen atom and the four pyrrole NHs of the former. The inclusion complexes pack into rods, displaying a unidirectional orientation. In turn, the rods form flat 2D-layers by alternating the orientation of their p-iodo substituents. The 2D layers stack on top of another, resulting in a head-to-head and tail-to-tail orientation of the complexes or their exclusive arrangement in a head-to-tail geometry. The dissimilar stacking of the layers yields two solvate polymorphs that are simultaneously present in the structures of the single crystals. The ratio of the two polymorph phases is regulated by the amount of acetonitrile added to the chloroform solutions from which the crystals grow. Halogen bonding interactions are highly relevant in the crystal lattices of the two polymorphs. We analyzed and characterized these interactions by means of density functional theory (DFT) calculations and several computational tools. Remarkably, single crystals of a solvate containing two acetonitrile molecules per calix[4]pyrrole were obtained from pure acetonitrile solution. eng Polymorphs Halogen bonds Supramolecular chemistry Lattice energies Density Functional Theory (DFT) calculations Synthesis, X-ray Characterization and Density Functional Theory (DFT) Studies of Two Polymorphs of the alpha,alpha,alpha,alpha, Isomer of Tetra-p-Iodophenyl Tetramethyl Calix[4]pyrrole: On the Importance of Halogen Bonds research article