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

Polymers

Pedro Villanueva-Delgado¹  Rafael Valiente²  Alla Dikhtiarenko³  José Gimeno³  José R. García³ 

[1] Department of Chemistry and Biochemistry, University of Bern, 3012 Bern, Switzerland;MALTA Consolider Team, Department of Applied Physic, University of Cantabria, 39005 Santander, Spain;Organic and Inorganic Chemistry Department, University of Oviedo-CINN, 33006 Oviedo, Spain;

关键词: water splitting;    hydrogen evolution;    coordination polymers;    photocatalysts;   

DOI  :  10.3390/polym8020048

来源: DOAJ

【 摘 要 】

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 1–8 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.

【 授权许可】

Unknown