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oai:uvadoc.uva.es:10324/615012025-03-04T12:37:41Zcom_10324_28542com_10324_952com_10324_894col_10324_28543

Modulating organic/inorganic segregation in columnar mesophases Domingo de la Rubia, Estela de García Moreno, Gregorio José Folcia, César L. Ortega, Josu Etxebarria, Jesús Coco Cea, Silverio Materials science Química inorgánica Producción Científica This work reports an uncommon modulation of columnar segregation of metal–organic triphenylene liquid crystals by blending two structurally dissimilar metallomesogens that can self-associate through complementary electron donor–acceptor interactions. The constituent molecules are cis-[PtCl2(CNR)2] (CNR = 2-(6-(4-isocyanophenoxy)hexyloxy)-3,6,7,10,11-pentakisdodecyloxytriphenylene) that displays an organic/inorganic segregated columnar mesophase and [PtCl2(Bipy)] (Bipy = didodecyl 2,2′-bipyridyl-4,4′-dicarboxylate) that shows a lamellar mesomorphism. The phase diagram of this system was constructed using polarized optical microscopy (POM), differential scanning calorimetry (DSC), and X-ray scattering data. The phase diagram corresponds to a typical binary system with an intermediate compound (in this case a supramolecular aggregate) of stoichiometry [PtCl2(CNR)2]/2[PtCl2(Bipy)], which is maintained in solution. This species shows an unusual columnar mesophase formed by the stacking of alternating organic/inorganic fragments. Quantum chemical calculations show that the columnar structure is mainly supported by complementary π electron donor–acceptor interactions between each triphenylene group of the isocyanide complex and a platinum-bipyridine molecule. This induces the elimination of the organic/inorganic columnar segregation of the isocyano parent component and constitutes an unconventional example of modulation of organic/inorganic segregation in columnar mesophases by the intercalation of metal complexes into hexaalkoxytriphenylene stacks. 2023-09-11T08:28:50Z 2023-09-11T08:28:50Z 2023 info:eu-repo/semantics/article Crystal Growth Design 2023, vol. 23, n. 9, pp. 6812–6821 1528-7483 https://uvadoc.uva.es/handle/10324/61501 10.1021/acs.cgd.3c00660 6812 9 6821 Crystal Growth & Design 23 1528-7505 eng https://pubs.acs.org/doi/full/10.1021/acs.cgd.3c00660 info:eu-repo/semantics/openAccess http://creativecommons.org/licenses/by/4.0/ © 2023 The Authors Atribución 4.0 Internacional American Chemical Society SI