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

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 f...

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Bibliographic Details
Published in:Chemistry : a European journal 2015-07, Vol.21 (28), p.10094-10099
Main Authors: González-Monje, Pablo, Novio, Fernando, Ruiz-Molina, Daniel
Format: Article
Language:English
Subjects:
2D assembly
Chemistry
coordination polymer
Coordination polymers
Gold
Grafting
Interphase
Nanoparticles
Photoelectron spectroscopy
Polymers
spin transition
surface assembly
valence tautomerism
X-ray photoelectron spectroscopy
X-rays
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Summary: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 at or around room temperature. SEM and AFM characterization reveal that the nanoparticles were organized chiefly into a single monolayer while X‐ray photoelectron spectroscopy (XPS) measurements confirm that the nanoparticles retain a temperature‐induced electronic redistribution upon surface anchorage. Our results represent an effective approach towards the challenging manufacture of coordination polymers. CPPs immobilization: A generic approach for immobilizing coordination polymer nanoparticles (CPPs) on gold surfaces is reported. The protocol involves covalent bonding between amino‐terminated alkyl chains on the gold surface and carboxylic groups on the CPPs surface. The thickness of the nanoparticle monolayer is comparable to the nanoparticle size. The nanoparticles used exhibit valence tautomerism in bulk and keep this property after surface attachment, as corroborated by X‐ray photoelectron spectroscopy (XPS) measurements. The results represent an effective approach towards the manufacture of coordination polymers.
ISSN:0947-6539
1521-3765
DOI:10.1002/chem.201500671