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Thermally Robust 1D Cu(I) Phosphonate Coordination Polymer Exhibiting Enhanced Proton Conductivity via Humidity‐Driven Pathways
- The development of thermally stable solid-state proton conductors (SSPCs) is crucial for advancing energy-conversion devices such as proton-exchange membrane fuel cells (PEMFCs). In this work, we report the solvothermal synthesis and characterization of a novel, 1D Cu(I) coordination polymer, {Cu(ADP)0.5(BPY)}n (BAM-5), based on anthracenediylphosphonate (H2ADP) and 4,40 -bipyridine (BPY). Single-crystal X-ray diffraction revealed that BAM-5 crystallizes in the triclinic space group P1 and shows a 1D ladder structure connected by the H2ADP and organic BPY linkers, which is assembled into a 2D layer via O−H···O hydrogen bonding interactions between uncoordinated oxygen and the O−H of the phosphonate group. Thermogravimetric and dynamic water sorption analysis demonstrated exceptional thermal robustness of BAM-5 until 230°C and notable water affinity. Proton conductivity measurements found increasing proton conductive properties with increasing temperature and relative humidity.TheThe development of thermally stable solid-state proton conductors (SSPCs) is crucial for advancing energy-conversion devices such as proton-exchange membrane fuel cells (PEMFCs). In this work, we report the solvothermal synthesis and characterization of a novel, 1D Cu(I) coordination polymer, {Cu(ADP)0.5(BPY)}n (BAM-5), based on anthracenediylphosphonate (H2ADP) and 4,40 -bipyridine (BPY). Single-crystal X-ray diffraction revealed that BAM-5 crystallizes in the triclinic space group P1 and shows a 1D ladder structure connected by the H2ADP and organic BPY linkers, which is assembled into a 2D layer via O−H···O hydrogen bonding interactions between uncoordinated oxygen and the O−H of the phosphonate group. Thermogravimetric and dynamic water sorption analysis demonstrated exceptional thermal robustness of BAM-5 until 230°C and notable water affinity. Proton conductivity measurements found increasing proton conductive properties with increasing temperature and relative humidity.The latter is correlated with the material’s water uptake since the structure itself does not contain any permanent lattice water molecules. A maximum proton conductivity of 6.6 × 10−6 S cm−1 was found at 80°C and 98% RH. To the best of our knowledge, no dense, nonporous 1D coordination polymer without lattice or coordinated solvent molecules has shown comparable proton con� ductivity. The high activation energy suggests a combination of both, a Grotthuss-type proton hopping through the hydrogen� bonded framework, and a vehicular process, in which protons are carried along with absorbed water molecules.…


| Autor*innen: | Alina SchmalzORCiD, Charles Gaston Eby, Caitlin Moss, Biswajit BhattacharyaORCiD, Franziska EmmerlingORCiD |
|---|---|
| Dokumenttyp: | Zeitschriftenartikel |
| Veröffentlichungsform: | Verlagsliteratur |
| Sprache: | Englisch |
| Titel des übergeordneten Werkes (Englisch): | Zeitschrift für anorganische und allgemeine Chemie |
| Jahr der Erstveröffentlichung: | 2025 |
| Organisationseinheit der BAM: | 6 Materialchemie |
| 6 Materialchemie / 6.0 Abteilungsleitung und andere | |
| 6 Materialchemie / 6.3 Strukturanalytik | |
| Veröffentlichende Institution: | Bundesanstalt für Materialforschung und -prüfung (BAM) |
| Verlag: | Wiley VHC-Verlag |
| Aufsatznummer: | e202500187 |
| Erste Seite: | 1 |
| Letzte Seite: | 8 |
| DDC-Klassifikation: | Technik, Medizin, angewandte Wissenschaften / Ingenieurwissenschaften / Ingenieurwissenschaften und zugeordnete Tätigkeiten |
| Freie Schlagwörter: | Coordination polymers; Phosphonate ligand; Proton conduction; X-ray diffraction |
| Themenfelder/Aktivitätsfelder der BAM: | Material |
| Material / Materialdesign | |
| DOI: | 10.1002/zaac.202500187 |
| URN: | urn:nbn:de:kobv:b43-651382 |
| ISSN: | 0044-2313 |
| Verfügbarkeit des Dokuments: | Datei für die Öffentlichkeit verfügbar ("Open Access") |
| Lizenz (Deutsch): | Creative Commons - CC BY - Namensnennung 4.0 International |
| Datum der Freischaltung: | 15.12.2025 |
| Referierte Publikation: | Ja |
| Datum der Eintragung als referierte Publikation: | 15.12.2025 |
| Schriftenreihen ohne Nummerierung: | Wissenschaftliche Artikel der BAM |


