Coordination polymers (CPs) are versatile materials formed by metal ions and organic ligands, offering a broad range of structural and functional possibilities. Phosphonates and phosphinates are particularly attractive ligands for CPs due to their multiple binding sites, varied coordination geometries, and ability to form robust network structures. Phosphonates, considered harder ligands, form strong bonds with hard metals such as Fe3+, while phosphinates offer additional versatility due to the varied pendant groups on phosphorus. This study presents a series of six new coordination polymers, ICR-20 and ICR-21, incorporating Fe2+, Co2+, and Ni2+ metal centers, using phosphinate (H2PBP-(Me)) or phosphinate-phosphonate (H3PPP-(Me)) ligands in combination with 4,4'-bipyridine. The materials are isoreticular despite the incorporation of different functional groups, demonstrating the interchangeability of the phosphinate and phosphonate groups in their design. These polymers were characterized structurally and investigated for their magnetic properties. The combination of local insights from Mössbauer spectroscopy and bulk magnetic data provides complex information on crystal field parameters and magnetic interactions in Fe-based polymers. Additionally, their proton conductivity was evaluated, showing promising results.

Center of Materials and Nanotechnologies Faculty of Chemical Technology University of Pardubice Cs Legii 565 530 02 Pardubice Czech Republic

Department of Inorganic Chemistry Faculty of Science Charles University Hlavova 2030 Prague 12840 Czech Republic

Faculty of Mathematics and Physics Charles University 5 Holešovičkách 2 180 00 Prague Czech Republic

Institute of Inorganic Chemistry of the Czech Academy of Sciences Husinec Řež 1001 250 68 Řež Czech Republic

Institute of Physics of the Czech Academy of Sciences Cukrovarnická 10 112 162 00 Prague Czech Republic

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