Related Experiment Video
Updated: Jun 23, 2025
Preparation of Polyoxometalate-based Photo-responsive Membranes for the Photo-activation of Manganese Oxide Catalysts
Published on: August 7, 2018
Reticular Imine-Linked Coordination Polymers Based on Paddlewheel Diruthenium/Dirhodium Nodes: Synthesis and
Chisa Itoh1,2, Masaki Kitada3, Mio Kondo3
1Institute for Materials Research, Tohoku University, 2-1-1 Katahira, Aoba-ku, Sendai, 980-8577, Japan.
Abstract:
The paddlewheel-type dimetal core ([M2]) is a ubiquitous motif in the nodes in coordination polymers (CPs) and metal-organic frameworks (MOFs). However, their preparation has relied on ligand-substitution-labile metal ions owing to challenges associated with crystallization. Consequently, examples featuring ligand-substitution-inert metal ions, such as Ru or Rh, are scarce. This study presents the synthesis of novel reticular imine-linked CPs incorporating the paddlewheel-type diruthenium(II, II) ([Ru2 II,II]; 1-Ru) or dirhodium(II, II) ([Rh2 II,II]; 1-Rh) subunits. The synthetic approach involved a Schiff base dehydration condensation reaction between p-formylbenzoate-bridged [Ru2 II,II] or [Rh2 II,II] precursors (i. e., CHO-Ru and CHO-Rh, respectively) and 2,5-dimethyl-1,4-phenylenediamine in a 1 : 2 ratio. The catalytic activities of 1-Ru and 1-Rh for the photochemical reduction of CO2 in a heterogeneous system depended on the metal site. The 1-Ru system exhibited exceptional selectivity, generating 3.0×104 μmol g-1 of CO after 24 h of irradiation, whereas the 1-Rh system generated a lower amount of CO (3.2×103 μmol g-1). The catalytic activity of 1-Ru ranked with that of all relevant catalytic systems. This study paves the way for the exploration of [Ru2 II,II]- or [Rh2 II,II]-based polymers with open metal site-dependent functional properties.
Related Concept Videos
02:17Reduction of Alkenes: Asymmetric Catalytic Hydrogenation
The metal catalyst used can be either heterogeneous or homogeneous. When hydrogenation of an alkene generates a chiral center, a pair of enantiomeric products is expected to form. However, an enantiomeric excess of one of the products can be facilitated using an enantioselective reaction or an...
02:34Structural Isomerism
Isomers are different chemical species that have the same chemical formula. Structural isomerism of coordination compounds can be divided into two subcategories, the linkage isomers and coordination-sphere isomers.
Linkage isomers occur when the coordination compound contains a ligand that can bind to the transition metal center through two different atoms. For example, the CN− ligand can bind through the carbon atom or through the nitrogen atom. Similarly, SCN− can...