Spin‐Crossover Grafted Monolayer of a Co(II) Terpyridine Derivative Functionalized with Carboxylic Acid Groups

Author:

García‐López Víctor12,Giaconi Niccolò2ORCID,Poggini Lorenzo3ORCID,Calbo Joaquín1ORCID,Juhin Amélie4ORCID,Cortigiani Brunetto2ORCID,Herrero‐Martín Javier5ORCID,Ortí Enrique1ORCID,Mannini Matteo2ORCID,Clemente‐León Miguel1ORCID,Coronado Eugenio1ORCID

Affiliation:

1. Instituto de Ciencia Molecular Universidad de Valencia Catedrático José Beltrán 2 46980 Paterna Spain

2. Department of Chemistry “Ugo Schiff” and INSTM Research Unit University of Florence Via della Lastruccia 3–13 50019 Sesto Fiorentino Italy

3. Istituto di Chimica dei Composti Organometallici (ICCOM) CNR Via Madonna del Piano, 10 50019 Sesto Fiorentino Italy

4. Institut de Minéralogie de Physique des Matériaux et de Cosmochimie (IMPMC) UMR7590 CNRS Sorbonne Université MNHN 4 Place Jussieu, Cedex 5 75252 Paris France

5. ALBA Synchrotron Carrer de la Llum 2–26 Cerdanyola del Vallès 08290 Barcelona Spain

Abstract

AbstractThe synthesis and characterization of a new Co(II) spin‐crossover (SCO) complex based on 4′‐(4‐carboxyphenyl)−2,2′:6′,2″‐terpyridine ligand are reported. This complex can be successfully grafted on silver surface maintaining the SCO behavior. Thus, atomic force microscopy (AFM), matrix assisted laser desorption ionization – time‐of‐flight mass spectrometry (MALDI‐TOF MS), Raman spectroscopy, and XPS measurements, upon surface deposition, evidence the formation of a monolayer of intact molecules grafted through carboxylate groups to the Ag surface. Three different techniques: Raman spectroscopy, X‐ray photoelectron spectroscopy (XPS), and X‐ray absorption spectroscopy (XAS), supported by first‐principles calculations, confirm that the deposited molecules undergo a gradual spin transition with temperature. This phenomenon is unprecedented for a monolayer of molecules directly grafted onto a metallic surface from solution.

Funder

European Commission

Generalitat Valenciana

Dipartimenti di Eccellenza

Fondazione Cassa di Risparmio di Firenze

Publisher

Wiley

Subject

Electrochemistry,Condensed Matter Physics,Biomaterials,Electronic, Optical and Magnetic Materials

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