Strong, Yet Split Hydrogen Bonding with Ice Rules in Delafossite (H/D)RhO2

Matthew A. Wright; Anya S. Mulligan; Dibyata Rout; Jerry G. Hu; Jue Liu; Rachel L. Behrens; Juan R. Chamorro; Stephen D. Wilson; Anthony K. Cheetham; Ram Seshadri

doi:10.1002/anie.202515471

Strong, Yet Split Hydrogen Bonding with Ice Rules in Delafossite (H/D)RhO₂

Matthew A. Wright
, Anya S. Mulligan
, Dibyata Rout
, Jerry G. Hu
, Jue Liu
, Rachel L. Behrens
, Juan R. Chamorro
, Stephen D. Wilson
, Anthony K. Cheetham
, Ram Seshadri

Research output: Contribution to journal › Article › peer-review

Abstract

Despite remaining enigmatic, strong hydrogen bonding provides an advanced design handle for tailoring the properties of functional materials. Here, 3R–(H/D)RhO₂ delafossites (prepared by ion exchange of Na⁺ from NaRhO₂) contain H/D in linear coordination with O, linking Rh^IIIO₂ layers. Bragg and real-space X-ray and neutron scattering analysis, vibrational and solid-state NMR spectroscopy, and density functional theory (DFT)–based electronic structure calculations have been employed to understand the nature of the hydrogen bonding. Despite short distances between H/D and the two O to which they are bonded, a clear double-minimum corresponding to a shorter and longer (H/D)–O distance is established. The triangular lattices formed by H/D appear to display ice-like disorder, corroborated by low-temperature heat capacity measurements.

Original language	English
Article number	e15471
Journal	Angewandte Chemie - International Edition
Volume	64
Issue number	52
DOIs	https://doi.org/10.1002/anie.202515471
State	Published - Dec 22 2025
Externally published	Yes

Funding

The authors thank Professor Clare Grey for useful suggestions regarding the NMR analysis. This research was supported by the Eddleman Centre for Quantum Innovation at UC Santa Barbara. DR and SDW acknowledge support from the US Department of Energy, Office of Science, Basic Energy Sciences under Award No. DE‐SC0017752. AKC thanks the Ras Al Khaimah Centre for Advanced Materials for financial support. The research reported here made use of the shared facilities of the Materials Research Science and Engineering Center (MRSEC) at UC Santa Barbara: NSF DMR–2308708. The UC Santa Barbara MRSEC is a member of the Materials Research Facilities Network ( www.mrfn.org ). The authors acknowledge a block allocation from the Diamond Light Source for access to beamline i‐11 under proposal CY36397 and the Spallation Neutron Source and JL at Oak Ridge National Laboratory for access to the Nanoscale‐Ordered Materials Diffractometer (NOMAD) under proposal number 32507.

Keywords

Density functional calculations
Hydrogen bonds
Materials science
NMR spectroscopy
Neutron diffraction

Access to Document

10.1002/anie.202515471

Cite this

@article{7296fb8984984398ad2bd52a93066d75,

title = "Strong, Yet Split Hydrogen Bonding with Ice Rules in Delafossite (H/D)RhO2",

abstract = "Despite remaining enigmatic, strong hydrogen bonding provides an advanced design handle for tailoring the properties of functional materials. Here, 3R–(H/D)RhO2 delafossites (prepared by ion exchange of Na+ from NaRhO2) contain H/D in linear coordination with O, linking RhIIIO2 layers. Bragg and real-space X-ray and neutron scattering analysis, vibrational and solid-state NMR spectroscopy, and density functional theory (DFT)–based electronic structure calculations have been employed to understand the nature of the hydrogen bonding. Despite short distances between H/D and the two O to which they are bonded, a clear double-minimum corresponding to a shorter and longer (H/D)–O distance is established. The triangular lattices formed by H/D appear to display ice-like disorder, corroborated by low-temperature heat capacity measurements.",

keywords = "Density functional calculations, Hydrogen bonds, Materials science, NMR spectroscopy, Neutron diffraction",

author = "Wright, \{Matthew A.\} and Mulligan, \{Anya S.\} and Dibyata Rout and Hu, \{Jerry G.\} and Jue Liu and Behrens, \{Rachel L.\} and Chamorro, \{Juan R.\} and Wilson, \{Stephen D.\} and Cheetham, \{Anthony K.\} and Ram Seshadri",

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month = dec,

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doi = "10.1002/anie.202515471",

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T1 - Strong, Yet Split Hydrogen Bonding with Ice Rules in Delafossite (H/D)RhO2

AU - Wright, Matthew A.

AU - Mulligan, Anya S.

AU - Rout, Dibyata

AU - Hu, Jerry G.

AU - Liu, Jue

AU - Behrens, Rachel L.

AU - Chamorro, Juan R.

AU - Wilson, Stephen D.

AU - Cheetham, Anthony K.

AU - Seshadri, Ram

PY - 2025/12/22

Y1 - 2025/12/22

N2 - Despite remaining enigmatic, strong hydrogen bonding provides an advanced design handle for tailoring the properties of functional materials. Here, 3R–(H/D)RhO2 delafossites (prepared by ion exchange of Na+ from NaRhO2) contain H/D in linear coordination with O, linking RhIIIO2 layers. Bragg and real-space X-ray and neutron scattering analysis, vibrational and solid-state NMR spectroscopy, and density functional theory (DFT)–based electronic structure calculations have been employed to understand the nature of the hydrogen bonding. Despite short distances between H/D and the two O to which they are bonded, a clear double-minimum corresponding to a shorter and longer (H/D)–O distance is established. The triangular lattices formed by H/D appear to display ice-like disorder, corroborated by low-temperature heat capacity measurements.

AB - Despite remaining enigmatic, strong hydrogen bonding provides an advanced design handle for tailoring the properties of functional materials. Here, 3R–(H/D)RhO2 delafossites (prepared by ion exchange of Na+ from NaRhO2) contain H/D in linear coordination with O, linking RhIIIO2 layers. Bragg and real-space X-ray and neutron scattering analysis, vibrational and solid-state NMR spectroscopy, and density functional theory (DFT)–based electronic structure calculations have been employed to understand the nature of the hydrogen bonding. Despite short distances between H/D and the two O to which they are bonded, a clear double-minimum corresponding to a shorter and longer (H/D)–O distance is established. The triangular lattices formed by H/D appear to display ice-like disorder, corroborated by low-temperature heat capacity measurements.

KW - Density functional calculations

KW - Hydrogen bonds

KW - Materials science

KW - NMR spectroscopy

KW - Neutron diffraction

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