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oai:riubu.ubu.es:10259/119932026-09-04T00:05:27Zcom_10259_4323com_10259_5086com_10259_2604col_10259_4330

2026-09-03T10:07:52Z urn:hdl:10259/11993 Competitive Hydrogen-Bond Partitioning in Deep Eutectic Solvents: From Cooperative Charge Spreading to Structure–Property Design Rules Huerta Sainz, Sergio de la Santamaría, Sara Escobedo Monge, María Antonieta Trenzado, José L. Diez Cabanes, Valentin Gutiérrez Vega, Alberto Marcos Villa, Pedro A. Bol Arreba, Alfredo Atilhan, Mert Aparicio Martínez, Santiago Mathematical methods Viscosity Solvents Physical and chemical properties Noncovalent interactions Deep eutectic solvents (DESs) owe their remarkable melting-point depression, high viscosity, and tunable solvation to a hydrogen-bond network far richer than the binary donor–acceptor picture suggests. This study advances the framework of competitive hydrogen-bond partitioning: ionic Cl–···H–X interactions, neutral donor–donor self-association, cation-mediated contacts, and water-competitive motifs coexist and continuously redistribute as a function of composition, temperature, and interfacial confinement. Evidence is synthesized from vibrational spectroscopy, multinuclear NMR, neutron and X-ray scattering, dielectric relaxation, classical and ab initio molecular dynamics, DFT cluster calculations, and machine-learning potentials, establishing that no single technique can fully characterize the network─a triangulation criterion requiring at least two independent method categories is essential. A quantitative structure–property framework is developed linking six hydrogen-bond descriptors─motif population, persistence distribution, network connectivity, competitive hydration index, dynamic heterogeneity, and interfacial partitioning─to viscosity, conductivity, diffusion, and glass transition across Type III, Type V, Natural DES (NADES), and hydrophobic DES. A central finding is the cooperativity–mobility tradeoff: cooperative charge spreading at Cl– simultaneously drives eutectic depression and network rigidity, defining a design axis along which DES can be rationally positioned. Water is analyzed as both competitive and cooperative partner across four hydration regimes, and interfacial hydrogen-bond reorganization at electrodes─largely neglected in prior studies─is critically examined. An integrated characterization workflow with standardized reporting criteria, validated force-field benchmarks, and data-driven descriptors for predictive screening is proposed. 2026-09-03T10:07:52Z 2026-09-03T10:07:52Z 2026-07 info:eu-repo/semantics/article 2470-1343 https://hdl.handle.net/10259/11993 10.1021/ACSOMEGA.6C02376 2470-1343 eng ACS Omega. 2026, V. 11, n. 26, p. 38868–38891 https://doi.org/10.1021/acsomega.6c02376?urlappend=%3Fref%3DPDF&jav=VoR&rel=cite-as http://creativecommons.org/licenses/by/4.0/ info:eu-repo/semantics/openAccess Atribución 4.0 Internacional ACS Publications