biostudies-literatureItoh CGrant Fund for Research and Education of Institute for Materials Research, Tohoku UniversityFUSO INNOVATIVE TECHNOLOGY FUNDShorai Foundation for Science and TechnologyInstitute for Materials Research, Tohoku UniversityMinistry of Education, Culture, Sports, Science, and Technology, JapanMinistry of Education, Culture, Sports, Science and TechnologyIzumi Science and Technology Foundatione202400885https://www.ebi.ac.uk/biostudies/studies/S-EPMC11632573biostudies-literatureUnknown17(23)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.ChemSusChemReticular Imine-Linked Coordination Polymers Based on Paddlewheel Diruthenium/Dirhodium Nodes: Synthesis and Metal-Site Dependent Photocatalytic Reduction of CO<sub>2</sub>.PMC1163257320K1529418H0520823K1789921H0190021K1892520H00381Kondo MMiyasaka HKonno TJKitada MYoshino HOotani YKosaka WMasaoka SMatsuda JKubo MItoh CfalseReticular Imine-Linked Coordination Polymers Based on Paddlewheel Diruthenium/Dirhodium Nodes: Synthesis and Metal-Site Dependent Photocatalytic Reduction of CO<sub>2</sub>.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.2024-01-01T00:00:00Z2024 Dec2025-04-26T16:09:11.324Z2025-04-06T15:09:42.775ZS-EPMC116325733889451210.1002/cssc.202400885