Phenoxyaluminum(salophen) Scaffolds: Synthesis, Electrochemical Properties, and Self-Assembly at Surfaces of Multifunctional Systems

MENGOZZI, Luca, EL GARAH, Mohamed, GUALANDI, Andrea, IURLO, Matteo, FIORANI, Andrea, CIESIELSKI, Artur, MARCACCIO, Massimo, PAOLUCCI, Francesco, SAMORÌ, Paolo et COZZI, Pier Giorgio, 2018. Phenoxyaluminum(salophen) Scaffolds: Synthesis, Electrochemical Properties, and Self-Assembly at Surfaces of Multifunctional Systems. Chemistry - A European Journal [en ligne]. 14 août 2018. Vol. 24, n° 46pp. 11954-11960. [Consultésans date]. DOI 10.1002/chem.201801118. Consulté de : https://doi.org/10.1002/chem.201801118Salophens and Salens are Schiff bases generated through the condensation of two equivalents of salicylaldehyde with either 1,2‐phenylenediamines or aliphatic diamines, respectively. Both ligands have been extensively exploited as key building blocks in coordination chemistry and catalysis. In particular, their metal complexes have been widely used for various catalytical transformations with high yield and selectivity. Through the modification of the phenol unit it is possible to tune the steric hindrance and electronic properties of Salophen and Salen. The introduction of long aliphatic chains in salicylaldehydes can be used to promote their self‐assembly into ordered supramolecular structures on solid surfaces. Herein, we report a novel method towards the facile synthesis of robust and air‐stable [Al(Salophen)] derivatives capable of undergoing spontaneous self‐assembly at the graphite/solution interface forming highly‐ordered nanopatterns. The new synthetic approach relies on the use of [MeAlIII(Salophen)] as a building unit to introduce, via a simple acid/base reaction with functionalized acidic phenol derivatives, selected frameworks integrating multiple functions for efficient surface decoration. STM imaging at the solid/liquid interface made it possible to monitor the formation of ordered supramolecular structures. In addition, the redox properties of the Salophen derivatives functionalized with ferrocene units in solution and on surface were unraveled by cyclic voltammetry. The use of a five‐coordinate aluminum alkyl Salophen precursor enables the tailoring of new Salophen molecules capable of undergoing controlled self‐assembly on HOPG, and thereby it can be exploited to introduce multiple functionalities with subnanometer precision at surfaces, ultimately forming ordered functional patterns.1. .
Accès restreint (30-09-2018) Peer reviewed
Version acceptée pour publication (post-print auteur)
Paternité - Pas d'utilisation commerciale [CC] [BY] [NC]
Auteurs Luca Mengozzi
Mohamed El Garah
Andrea Gualandi
Matteo Iurlo
Andrea Fiorani
Artur Ciesielski
Massimo Marcaccio
Francesco Paolucci
Paolo Samorì
Pier Giorgio Cozzi
Unité de recherche du site

Institut de Science et d'Ingénierie Supramoléculaires - ISIS - UMR7006
URL éditeur https://doi.org/10.1002/chem.201801118
Langue

en
Volume

24
Numéro

46
Page de début

11954
Page de fin

11960
Date de première publication

2018-03-30
Date de parution

2018-08-14
ISSN

09476539
Titre de la source (revue, livre…)

Chemistry - A European Journal
Résumé

Salophens and Salens are Schiff bases generated through the condensation of two equivalents of salicylaldehyde with either 1,2‐phenylenediamines or aliphatic diamines, respectively. Both ligands have been extensively exploited as key building blocks
Show moreSalophens and Salens are Schiff bases generated through the condensation of two equivalents of salicylaldehyde with either 1,2‐phenylenediamines or aliphatic diamines, respectively. Both ligands have been extensively exploited as key building blocks in coordination chemistry and catalysis. In particular, their metal complexes have been widely used for various catalytical transformations with high yield and selectivity. Through the modification of the phenol unit it is possible to tune the steric hindrance and electronic properties of Salophen and Salen. The introduction of long aliphatic chains in salicylaldehydes can be used to promote their self‐assembly into ordered supramolecular structures on solid surfaces. Herein, we report a novel method towards the facile synthesis of robust and air‐stable [Al(Salophen)] derivatives capable of undergoing spontaneous self‐assembly at the graphite/solution interface forming highly‐ordered nanopatterns. The new synthetic approach relies on the use of [MeAlIII(Salophen)] as a building unit to introduce, via a simple acid/base reaction with functionalized acidic phenol derivatives, selected frameworks integrating multiple functions for efficient surface decoration. STM imaging at the solid/liquid interface made it possible to monitor the formation of ordered supramolecular structures. In addition, the redox properties of the Salophen derivatives functionalized with ferrocene units in solution and on surface were unraveled by cyclic voltammetry. The use of a five‐coordinate aluminum alkyl Salophen precursor enables the tailoring of new Salophen molecules capable of undergoing controlled self‐assembly on HOPG, and thereby it can be exploited to introduce multiple functionalities with subnanometer precision at surfaces, ultimately forming ordered functional patterns.
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DOI 10.1002/chem.201801118
Éditeur

Wiley
Titre abrégé de la source

Chem. Eur. J.
Type de publication

ACL
Projet(s) de recherche ANR

LabEx project Chemistry of Complex Systems (ANR‐10‐LABX‐0026_CSC)
Projet(s) de recherche européen(s)

European Community through the project EC FP7 ICT‐MOLARNET (318516) and the European Research Council project SUPRAFUNCTION (GA‐257305)
Domaine

Chimie/Matériaux
Mots-clés

cyclic voltammetry
HOPG
salophen
self-assembly
STM microscopy
PMID 29603481
Unité de recherche extérieure au site

Dipartimento di Chimica “G. Ciamician” ALMA MATER STUDIORUM Università di Bologna Via Selmi 2, 40126, Bologna,Italy.
Fonction

aut
Identifiant ORCID 0000-0001-6256-8281
Audience

International