Surface induces different crystal structures in a room temperature switchable spin crossover compound

Denis Gentili; Fabiola Liscio; Nicola Demitri; Bernhard Schäfer; Francesco Borgatti; Piero Torelli; Benoit Gobaut; Giancarlo Panaccione; Giorgio Rossi; Alessandra Degli Esposti; Massimo Gazzano; Silvia Milita; Ilaria Bergenti; Giampiero Ruani; Ivan Šalitroš; Mario Ruben; Massimiliano Cavallini

doi:10.1039/C5DT03712C

Surface induces different crystal structures in a room temperature switchable spin crossover compound†

Denis Gentili,^a Fabiola Liscio,^b Nicola Demitri,^c Bernhard Schäfer,^d Francesco Borgatti,^a Piero Torelli,^e Benoit Gobaut,^c Giancarlo Panaccione,^e Giorgio Rossi,^ef Alessandra Degli Esposti,^g Massimo Gazzano,^g Silvia Milita,^b Ilaria Bergenti,^a Giampiero Ruani,^a Ivan Šalitroš,^h Mario Ruben^di and Massimiliano Cavallini*^a

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^a Consiglio Nazionale delle Ricerche, Istituto per lo Studio dei Materiali Nanostrutturati (CNR-ISMN) Via P. Gobetti 101, 40129 Bologna, Italy
E-mail: massimiliano.cavallini@cnr.it

^b Consiglio Nazionale delle Ricerche, Istituto per la Microelettronica e Microsistemi, (CNR-IMM) Via P. Gobetti 101, 40129 Bologna, Italy

^c Elettra – Sincrotrone Trieste, S.S. 14 Km 163.5 in Area Science Park, 34149 Basovizza – Trieste, Italy

^d Institute of Nanotechnology, Karlsruhe Institute of Technology, D-76344 Eggenstein-Leopoldshafen, Denmark

^e Consiglio Nazionale delle Ricerche, Istituto Officina dei Materiali (CNR-IOM), Laboratorio TASC, Area Science Park, I-34149 Trieste, Italy

^f Universita` di Milano, Dipartimento di Fisica, via Celoria 16, 20133 Milano, Italy

^g Consiglio Nazionale delle Ricerche, Istituto per la Sintesi Organica e la Fotoreattività (CNR-ISOF) Via P. Gobetti 101, 40129 Bologna, Italy

^h Institute of Inorganic Chemistry, Technology and Materials, Faculty of Chemical and Food Technology, Slovak University of Technology, Bratislava, Slovakia

ⁱ Institut de Physique et Chimie des Matériaux de Strasbourg (IPCMS), CNRS-Université de Strasbourg, 23, rue du Loess, BP 43, 67034, Strasbourg Cedex 2, France

Abstract

We investigated the influence of surfaces in the formation of different crystal structures of a spin crossover compound, namely [Fe(L)₂] (LH: (2-(pyrazol-1-yl)-6-(1H-tetrazol-5-yl)pyridine), which is a neutral compound thermally switchable around room temperature. We observed that the surface induces the formation of two different crystal structures, which exhibit opposite spin transitions, i.e. on heating them up to the transition temperature, one polymorph switches from high spin to low spin and the second polymorph switches irreversibly from low spin to high spin. We attributed this inversion to the presence of water molecules H-bonded to the complex tetrazolyl moieties in the crystals. Thin deposits were investigated by means of polarized optical microscopy, atomic force microscopy, X-ray diffraction, X-ray absorption spectroscopy and micro Raman spectroscopy; moreover the analysis of the Raman spectra and the interpretation of spin inversion were supported by DFT calculations.

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Surface induces different crystal structures in a room temperature switchable spin crossover compound†

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Surface induces different crystal structures in a room temperature switchable spin crossover compound

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