Immobilization of Polyoxometalates on Tailored Polymeric Surfaces

Aguado-Ureta, Saioa; Rodríguez‐Hernández, Juan; Campo, Adolfo del; Pérez‐Álvarez, Leyre; Vilas, José Luis; Reinoso, Santiago; Gutiérrez‐Zorrilla, Juan M.

doi:10.3390/nano8030142

Cited by 6 publications

(9 citation statements)

References 72 publications

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“…Synthesis of the diblock copolymer PS-b-PAA was carried out by atom transfer radical polymerization (ATRP) following previously reported procedures [37]. In brief, a polystyrene macroinitiator ([M]/[I]/[CuBr]/[L] = 50:1:1:1 where M = styrene; I = initiator, ethyl-2-bromoisobutyrate; and L = ligand, N,N,N′,N′′,N′′‒pentamethyldiethtylentriamine, PMDETA) was synthesized under N 2 at 65 °C after degassing the reaction mixture by three freeze‒pump‒thaw cycles.…”

Section: Methodsmentioning

confidence: 99%

“…Some other authors have opted for combining metal-substituted POMs that have exposed and accessible centers with solid substrates bearing functional groups that have coordinating ability [35,36]. Following the coordinative strategy, some of us reported [37] a very facile approach to incorporate lanthanide-containing Keggin-type [Ln III (SiW 11 O 39 )] 5− (Ln = Ce, Er) species on spin-coated polystyrene-b-poly(acrylic acid)/polystyrene (PS-b-PAA/PS) films. Polymeric surfaces were functionalized through interfacial migration of carboxylate groups upon water annealing.…”

Section: Introductionmentioning

confidence: 99%

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

et al. 2019

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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.

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Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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

et al. 2019

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“…16,17,18 Furthermore their functionalization by grafted or ionically associated organic moieties 19 enlarge the scope of applications 20 to for example molecular electronic, 21 photochromism 22,23,24 or surface anchoring. 25 The reactivity of the [Ir] + complex towards POMs is a very versatile system that allows designing a wide range of new other supramolecular assemblies by varying numerous synthesis parameters such as the nature of the POMs used, the [Ir] + /POM ratio, temperature and pressure, as well as the nature of solvents and additional counter -cations.…”

Section: Introductionmentioning

confidence: 99%

“…POMs are considered as nanosized molecular metal-oxide anions. They are built from the connection of {MO x } polyhedra, M being a d-block element in high oxidation state (V IV,V , Mo V,VI , W VI ), possess a wide range of sizes, shapes and charges, and exhibit various properties from catalysis, , medecine , to magnetism. − Furthermore, their functionalization by grafted or ionically associated organic moieties enlarge the scope of applications to for example molecular electronic, photochromism, − or surface anchoring . Our recent investigation of the [Ir] + /POM system led to the elaboration of five hybrid crystallized assemblies, namely, [Ir] 2 (TBA) 2 [β-Mo 8 O 26 ]-A, [Ir] 2 (TBA) 2 [β-Mo 8 O 26 ]-B, [Ir] 4 [α-Mo 8 O 26 ], [Ir] 2 [Mo 4 O 10 (OCH 3 ) 6 ]·2CH 3 OH, and [Ir] 2 [W 6 O 19 ] (labeled as t -Ir 2 W 6 -1 in the present work) .…”

Section: Introductionmentioning

confidence: 99%

“…16−18 Furthermore, their functionalization by grafted or ionically associated organic moieties 19 enlarge the scope of applications 20 to for example molecular electronic, 21 photochromism, 22−24 or surface anchoring. 25 Our recent investigation of the [Ir] + /POM system led to the elaboration of five hybrid crystallized assemblies, namely, green to yellow, orange, orange-red, and red, without any prior ligand functionalization but only by playing with the nature of the POM unit and the crystal packing mode. Such hybrid systems can also exhibit remarkable vapoluminescence properties useful for the detection of selective volatile organic compounds (VOCs), and thus even in the presence of moisture.…”

Section: Introductionmentioning

confidence: 99%

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Polymorphism and Structural Filiations in Five New Organic–Inorganic Hybrid Salts of the Heteroleptic Cationic Iridium(III) Complex and Polyoxometalates

Bolle

Serier‐Brault

Boulmier

et al. 2018

Crystal Growth & Design

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Five new hybrid compounds ionically associating the phosphorescent heteroleptic cationic iridium(III) complex [Ir III (ppy)2(bpy)] + ([Ir] + ) (ppy = 2-phenylpyridine, bpy = 2,2'-bipyridine) and anionic polyoxometalates (POMs) units have been successfully elaborated, namelyand [Ir]2(HDMA)2[-Mo8O26]•2DMF•H2O (HDMA + = dimethylammonium) (Ir2Mo8HDMA). These systems differ by the composition and the topology of the POMs, the [Ir] + /POM ratio, the nature of the other counter-cations, and the presence or not of crystallized solvent molecules. Their crystal structures and their photoluminescent properties have been determined and compared with those of a previously reported series of [Ir] + /POM assemblies revealing polymorphism and structural filiations. The emission properties of the compounds are strongly modulated by the nature of the POM units and the crystal packing of the hybrid frameworks.

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Polyoxometalate‐Soft Matter Composite Materials: Design Strategies, Applications, and Future Directions

Kruse

Langer

Romanenko

et al. 2022

Adv Funct Materials

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Molecular metal oxides, or polyoxometalates (POMs) offer unrivalled properties in areas ranging from catalysis and energy conversion through to molecular electronics, biomimetics and theranostics. While POMs are ubiquitous metal oxide model systems studied in most areas of chemistry and materials science, their technological deployment is often hampered by their molecular nature, as this leads to increased degradation, leaching and loss of reactivity, particularly when harsh applications, such as water electrolysis, thermal catalysis or highly basic/acidic reaction solutions are targeted. Therefore, immobilization of POMs on heterogeneous substrates has recently become a central theme in POM research. While early studies focused mainly on metal oxide and semiconductor supports, more recently, POM integration in soft matter matrices including polymers, conductive polymers, hydrogels and stimuliresponsive matrices have led to breakthroughs in multifunctional composite design. This Progress Report will summarize the recent pioneering studies in this emerging field, highlight current challenges which need to be overcome to allow a more widespread technological deployment and provide the authors' view of some of the most promising future directions of the research field. In addition, we provide an unprecedented summary of the correlations between structure (on the molecular, nano-and microscale) and resulting reactivity, so that materials design beyond empirical studies can be further developed. We believe that this timely Progress Report will serve as a focal point to further develop the field, as well as point of reference for newcomers in the area of knowledge-driven bottom up materials design. Given this broad range of interest groups, we believe that Advanced Functional Materials is the ideal journal for this Progress Report.

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Immobilization of Polyoxometalates on Tailored Polymeric Surfaces

Cited by 6 publications

References 72 publications

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

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

Polymorphism and Structural Filiations in Five New Organic–Inorganic Hybrid Salts of the Heteroleptic Cationic Iridium(III) Complex and Polyoxometalates

Polyoxometalate‐Soft Matter Composite Materials: Design Strategies, Applications, and Future Directions

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