Covalent Grafting of Coordination Polymers on Surfaces: The Case of Hybrid Valence Tautomeric Interphases

Abstract

We have developed a novel approach for grafting coordination polymers, structured as nanoparticles bearing surface reactive carboxylic groups, to amino-functionalized surfaces through a simple carbodiimide-mediated coupling reaction. As a proof-of concept to validate our approach and on the quest for novel hybrid interphases with potential technological applications, we have used valence tautomeric nanoparticles exhibiting spin transition around room temperature. SEM and AFM characterization reveal that the nanoparticles were organized chiefly into a single monolayer while XPS measurements confirm that the nanoparticles retain a temperature-induced electronic redistribution upon surface anchorage. Our results represent an effective approach towards the challenging manufacturing of coordination polymers.

Switchable cobalt coordination polymers: Spin crossover and valence tautomerism

“…However, this is not at all the case and 1D CPs have proved to be eminently suitable to form gels, fibres, films, nanoparticles and microspheres, and for grafting onto surfaces [42]. Very recently, following successful attempts with discrete VT coordination complexes [75,76] and iron SCO nanoparticles [43], attention has been brought to the synthesis of selfassembled monolayers of VT CP particles [72].…”

Design and Synthesis of a Noninnocent Multitopic Catechol and Pyridine Mixed Ligand: Nanoscale Polymers and Valence Tautomerism

“…5 Complexes of this family, termed as valence tautomers (VTs), have been proposed as potential building blocks to obtain molecular switching devices, where the ultimate goal is to manipulate information at the molecular level, build sensors, or display devices. 6 Most of the VT complexes thus far reported are monomeric 7 and dimeric 8 cobalt complexes containing quinone or quinonetype ligands. They are "noninnocent" electroactive ligands that may interconvert between the semiquinone SQ − and catecholate Cat 2− forms in response to an external stimulus (e.g., temperature).…”

Switchable colloids, thin-films and interphases based on metal complexes with non-innocent ligands: the case of valence tautomerism and their applications

“…Recently, we described an alternative approach for the organisation of VT-active compounds on surfaces based on the anchoring of VT-CPPs (described in Section 3) to a suitably functionalised surface. 36 For this, VT-CPPs bearing free carboxylic acid groups on their surface (B130 nm in diameter) were obtained upon combination of the polymerising ligand bix with the electroactive Co(3,5-dhcSQ)(3,5-dhcCat) units, where 3,5-dhcSQ À and 3,5-dhcCat 2À are the semiquinonate radical and catecholate forms of 3,4-dihydroxycinnamic acid (dhc), respectively (Fig. 13a).…”