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Polymers 2016, 8(2), 48; doi:10.3390/polym8020048

Tris(bipyridine)Metal(II)-Templated Assemblies of 3D Alkali-Ruthenium Oxalate Coordination Frameworks: Crystal Structures, Characterization and Photocatalytic Activity in Water Reduction

1
Organic and Inorganic Chemistry Department, University of Oviedo-CINN, 33006 Oviedo, Spain
2
Department of Chemistry and Biochemistry, University of Bern, 3012 Bern, Switzerland
3
MALTA Consolider Team, Department of Applied Physic, University of Cantabria, 39005 Santander, Spain
*
Authors to whom correspondence should be addressed.
Academic Editor: Félix Zamora
Received: 5 January 2016 / Revised: 27 January 2016 / Accepted: 4 February 2016 / Published: 15 February 2016
(This article belongs to the Special Issue Coordination Polymers: New Materials for Multiple Applications)
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Abstract

A series of 3D oxalate-bridged ruthenium-based coordination polymers with the formula of {[ZII(bpy)3][MIRu(C2O4)3]}n (ZII = Zn2+ (1), Cu2+ (3, 4), Ru2+ (5, 6), Os2+ (7, 8); MI = Li+, Na+; bpy = 2,2’-bipyridine) and {[ZnII(bpy)3](H2O)[LiRu(C2O4)3]}n (2) has been synthesized at room temperature through a self-assembly reaction in aqueous media and characterized by single-crystal and powder X-ray diffraction, elemental analysis, infrared and diffuse reflectance UV–Vis spectroscopy and thermogravimetric analysis. The crystal structures of all compounds comprise chiral 3D honeycomb-like polymeric nets of the srs-type, which possess triangular anionic cages where [ZII(bpy)3]2+ cationic templates are selectively embedded. Structural analysis reveals that the electronic configuration of the cationic guests is affected by electrostatic interaction with the anionic framework. Moreover, the MLCT bands gaps values for 18 can be tuned in a rational way by judicious choice of [ZII(bpy)3]2+ guests. The 3D host-guest polymeric architectures can be used as self-supported heterogeneous photocatalysts for the reductive splitting of water, exhibiting photocatalytic activity for the evolution of H2 under UV light irradiation. View Full-Text
Keywords: water splitting; hydrogen evolution; coordination polymers; photocatalysts water splitting; hydrogen evolution; coordination polymers; photocatalysts
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This is an open access article distributed under the Creative Commons Attribution License which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. (CC BY 4.0).

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MDPI and ACS Style

Dikhtiarenko, A.; Villanueva-Delgado, P.; Valiente, R.; García, J.R.; Gimeno, J. Tris(bipyridine)Metal(II)-Templated Assemblies of 3D Alkali-Ruthenium Oxalate Coordination Frameworks: Crystal Structures, Characterization and Photocatalytic Activity in Water Reduction. Polymers 2016, 8, 48.

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