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 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.
Highlights
In recent years, the depletion of fossil fuels and the environmental problems caused by their combustion have stimulated research on the development of new renewable energy production technologies
Metal-organic frameworks (MOFs) and coordination polymers (CPs) [5], which are organic–inorganic hybrid materials consisting of organic linkers and metal centers, clusters or metal-oxo clusters, have received great interest due to properties, such as extremely high surface areas, well-ordered porous architectures and structural designability [6,7]
We present the synthesis of a series of new three-dimensional ruthenium-based oxalate-bridged anionic networks {[MI RuIII (C2 O4 )3 ]2 ́ }n (MI = Na+, Li+ ) in which the large honeycombed channels are occupied by [ZII3 ]2+ cationic templates
Summary
The depletion of fossil fuels and the environmental problems caused by their combustion have stimulated research on the development of new renewable energy production technologies. Enormous attention has been paid to photocatalytic hydrogen production from water, which is a promising way to produce hydrogen as a potential clean energy source [1,2] In this line, the hybridization of organic and inorganic materials opens up a new field in the design and preparation of applicable photocatalysts for water splitting reaction by the integration of useful organic and inorganic characteristics within a single composite [3,4]. The hybridization of organic and inorganic materials opens up a new field in the design and preparation of applicable photocatalysts for water splitting reaction by the integration of useful organic and inorganic characteristics within a single composite [3,4] In this sense, metal-organic frameworks (MOFs) and coordination polymers (CPs) [5], which are organic–inorganic hybrid materials consisting of organic linkers and metal centers, clusters or metal-oxo clusters, have received great interest due to properties, such as extremely high surface areas, well-ordered porous architectures and structural designability [6,7]. In addition to a thorough structural characterization, we demonstrate the high photocatalytic activity of these structured solids
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