title: Understanding the Influence of the Electronic Structure on the Crystal Structure of a TTF-PTM Radical Dyad.
abstract: The understanding of the crystal structure of organic compounds, and its relationship to their physical properties, have become essential to design new advanced molecular materials. In this context, we present a computational study devoted to rationalize the different crystal packing displayed by two closely related organic systems based on the TTF-PTM dyad (TTF = tetrathiafulvalene, PTM = polychlorotriphenylmethane) with almost the same molecular structure but a different electronic one. The radical species (1), with an enhanced electronic donor-acceptor character, exhibits a herringbone packing, whereas the nonradical protonated analogue (2) is organized forming dimers. The stability of the possible polymorphs is analyzed in terms of the cohesion energy of the unit cell, intermolecular interactions between pairs, and molecular flexibility of the dyad molecules. It is observed that the higher electron delocalization in radical compound 1 has a direct influence on the geometry of the molecule, which seems to dictate its preferential crystal structure.
authors.affiliation: Laboratoire de Chimie Quantique, UMR-7177, CNRS-Université de Strasbourg , 4 rue Blaise Pascal, F-67000 Strasbourg, France.
authors.forename: Sergi
authors.identifier: http://orcid.org/0000-0002-3431-2470
authors.initials: S
authors.lastname: Vela
authors.affiliation: Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)/CIBER-BBN, Campus de la UAB, 08193, Bellaterra, Spain.
authors.forename: Manuel
authors.initials: M
authors.lastname: Souto
authors.affiliation: Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)/CIBER-BBN, Campus de la UAB, 08193, Bellaterra, Spain.
authors.forename: Imma
authors.initials: I
authors.lastname: Ratera
authors.affiliation: Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)/CIBER-BBN, Campus de la UAB, 08193, Bellaterra, Spain.
authors.forename: Concepció
authors.initials: C
authors.lastname: Rovira
authors.affiliation: Institut de Ciència de Materials de Barcelona (ICMAB-CSIC)/CIBER-BBN, Campus de la UAB, 08193, Bellaterra, Spain.
authors.forename: Jaume
authors.identifier: http://orcid.org/0000-0003-1023-9923
authors.initials: J
authors.lastname: Veciana