title: Origin of Bistability in the Butyl-Substituted Spirobiphenalenyl-Based Neutral Radical Material.
abstract: One of the most remarkable bistable materials reported so far is made of π dimers of a butyl-substituted spirobiphenalenyl boron radical (butyl-SBP). The phase transition of this material, which is accompanied by changes in its optical, conductive, and magnetic properties, occurs with a hysteretic loop 25 K wide centered at 335 K. Herein, a computational study is presented aimed at deciphering the origin of this hysteresis. The phase transition of butyl-SBP consists of a spin transition of the constituent π dimers coupled with an order-disorder transition involving the butyl chains linked to the nitrogen atoms of the superimposed phenalenyl rings of the π dimer. Below 335 K, the terminal methyl group of the butyl chains adopts a gauche conformation with respect to the methylene unit bonded to the nitrogen atom. Above 335 K, the methyl group is in an anti conformation and exhibits dynamic disorder. The gauche→anti conformational rearrangement triggers the spin transition of the π dimers and is responsible for the hysteretic behavior of butyl-SBP. Specifically, the onset of the phase transition in the heating mode, and thus, the width of the hysteresis loop, are governed by the high energy cost and strong structural cooperative effects associated with this conformational change. Our results show that coupling a spin switch with a conformational switch in a molecular crystal provides a promising strategy in the design of new bistable materials.
authors.affiliation: Departament de Química Física and IQTCUB, Facultat de Química, Universitat de Barcelona, Av. Diagonal 645, 08028, Barcelona, Spain.|Current address: Laboratoire de Chimie Quantique, Institut de Chimie UMR7177, CNRS-Université de Strasbourg, 1 Rue Blaise Pascal BP 296/R8, 67007, Strasbourg, France.
authors.forename: Maria
authors.identifier: http://orcid.org/0000-0002-4175-8876
authors.initials: M
authors.lastname: Fumanal
authors.affiliation: Departament de Química Física and IQTCUB, Facultat de Química, Universitat de Barcelona, Av. Diagonal 645, 08028, Barcelona, Spain.
authors.forename: Juan J
authors.identifier: http://orcid.org/0000-0003-3577-1182
authors.initials: JJ
authors.lastname: Novoa
authors.affiliation: Departament de Química Física and IQTCUB, Facultat de Química, Universitat de Barcelona, Av. Diagonal 645, 08028, Barcelona, Spain.
authors.forename: Jordi
authors.identifier: http://orcid.org/0000-0003-4088-6187
authors.initials: J
authors.lastname: Ribas-Arino
keywords: ab initio calculations; bistable materials; radicals; spin crossover; spiro compounds