Toward Advanced Functional Systems: Honeycomb-Like Polymeric Surfaces Incorporating Polyoxovanadates with Surface-Appended Copper-Cyclam Complexes.

Leyre Pérez-Álvarez,Beñat Artetxe,Tatsumi Ishihara,Leire Ruiz-Rubio,Jagoba Martín-Caballero,José Luis Vilas-Vilela,Juan M Gutiérrez-Zorrilla

doi:10.3390/molecules24122313

Abstract

In this work the immobilization of hybrid polyoxometalates (POMs) onto functional polymeric surfaces is exposed and discussed. Thus, various hybrid polymer‒inorganic films were prepared by anchoring selected hybrid POMs onto tailored polymeric surfaces that consisted of breath figures (BFs) made of polystyrene-b-poly(acrylic acid)/polystyrene (PS-b-PAA/PS) blends. Functionalization of the BF films was performed by selective arrangement of acrylic acid groups of the amphiphilic block copolymer on the surface pores because of their affinition for the water condensed during breath figure formation. These carboxylic acid functional groups contained within the PAA blocks were then employed to anchor [Cu(cyclam)][{Cu(cyclam)}2(V10O28)]·10H2O (1-CuV10) and [{Cu(cyclam)}(VO3)2]·5H2O (1-CuV1), hybrid POMs by immersing the films into aqueous solutions of the in situ formed hybrid clusters, resulting in the hybrid films BF1 and BF2, respectively. Superficial analysis of these hybrid polymeric films was carried out by the sophisticated ion beam-based technique time-of-flight secondary ion mass spectrometry (ToF-SIMS) that was revealed to be an excellent method for the superficial compositional mapping of patterned surfaces.

Highlights

Preparation of functional polyoxometalate (POM)-based materials is one of the hot topics within the chemistry of this family of nanometric metal-oxo clusters
We focused our studies on polyoxovanadate species appended with copper(II) complexes of N-donor ligands as simple models of hybrid POM–metalorganic systems
SEMimage imageofof example honeycomb patterns obtained by anan example of of thethe honeycomb patterns obtained by the the static breath figure methods at relative humidity (RH)

Summary

Introduction

Preparation of functional polyoxometalate (POM)-based materials is one of the hot topics within the chemistry of this family of nanometric metal-oxo clusters They have outstanding properties and are applicable in current issues of interest related to technology, health, energy, and the environment [1,2,3]. Despite their potential, direct preparation of such materials has been rather scarce because POMs usually present as crystalline solids that are hard to process. When it comes to polymeric materials, it has been shown that they can be covalently included in either polymer backbones or pending side chains and act as crosslinking units [11,12]

Methods

Results

Conclusion