A permanently porous chalcogen-bonded organic framework

Brian J. Eckstein; Hannah R. Martin; Michael P. Moghadasnia; Arijit Halder; Parker S. Brodale; Pierre Le Magueres; Patrick W.V. Butler; Katherine A. Forrest; Logan Ritter; Ryan A. Klein; Hyun June Moon; Cheng Li; Scott E. Massimi; Yongqiang Cheng; Christopher H. Hendon; Graeme M. Day; Brian Space; Craig M. Brown; C. Michael McGuirk

doi:10.1038/s44160-026-01072-x

A permanently porous chalcogen-bonded organic framework

Brian J. Eckstein
, Hannah R. Martin
, Michael P. Moghadasnia
, Arijit Halder
, Parker S. Brodale
, Pierre Le Magueres
, Patrick W.V. Butler
, Katherine A. Forrest
, Logan Ritter
, Ryan A. Klein
, Hyun June Moon
, Cheng Li
, Scott E. Massimi
, Yongqiang Cheng
, Christopher H. Hendon
, Graeme M. Day
, Brian Space
, Craig M. Brown
, C. Michael McGuirk

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

Abstract

The nature of connectivity between constituent atomic or molecular building blocks is fundamental in shaping the properties and functionality of materials. The extrapolation of emergent interatomic interactions to enable functional materials has driven transformative technological advancements. However, the bonding interactions used in material design have been largely static since the emergence of dynamic covalent chemistry ~30 years ago. Here we demonstrate that non-covalent chalcogen bonding (Ch-bonding) is a distinct mode of interatomic connectivity for constructing functional materials by design. This is established by leveraging self-complementary assembly of 1,2,5-telluradiazole moieties to construct a honeycomb-type permanently porous Ch-bonded organic framework, assembled and stabilized solely through non-covalent Te···N contacts. Empirical and computational studies of electronic structure, structural healing and lattice dynamics highlight the π-type electronic communication, controlled assembly and modulated lattice dynamics in Trip3Tez-I arising directly from the unique nature of the Te···N Ch-bonding that holds substantial implications for next generation crystalline semiconductors. In addition to introducing a distinct class of permanently porous frameworks, this work establishes Ch-bonding as a programmable molecular tool for constructing functional materials with distinct properties. (Figure presented.).

Original language	English
Journal	Nature Synthesis
DOIs	https://doi.org/10.1038/s44160-026-01072-x
State	Accepted/In press - 2026

Funding

National Science Foundation, Division of Materials Research, grant number 2143623 (B.J.E., H.R.M., M.P.M., A.H., S.E.M., C.M.M.); US Department of Energy (DOE) Office of Energy Efficiency and Renewable Energy, Hydrogen and Fuel Cell Technologies Office, contract number DE-AC36-8GO28308 to the National Renewable Energy Laboratory (R.A.K.); Laboratory Directed Research and Development program and Compute and Data Environment for Sciences (CADES) at ORNL (Y.C.); Hydrogen and Fuel Cell Technologies and Vehicle Technologies Office within the US DOE’s Office of Energy Efficiency and Renewable Energy, award number DE-EE0008812 (K.A.F., L.R., B.S.); National Science Foundation, grant number 2154882 (B.S.); National Institute of Standards and Technology (NIST, Department of Commerce) fully supported C.M.B., supported H.J.M. through cooperative agreement number 70NANB20H133 and partially supported work conducted by H.J.M. and R.A.K. while in residence at NIST; National Science Foundation, Division of Materials Research, grant number DMR-1956403 (P.S.B., C.H.H.); Research Corporation for Science Advancement, Cottrell Award (P.S.B., C.H.H.) and University of Southampton, Presidential PhD Scholarship (P.W.V.B.). A portion of the neutron scattering and gas dosing experiments used resources at the Spallation Neutron Source, a DOE Office of Science User Facility operated by the ORNL. A portion of the neutron scattering was funded by NIST. The computing resources for the NVS analysis were made available through the VirtuES project, funded by Laboratory Directed Research and Development program and CADES at ORNL. K.A.F. and B.S. gratefully acknowledge the computing resources provided by North Carolina State University High Performance Computing Services Core Facility (RRID:SCR_022168). B.S. acknowledges Bridges-2 at Pittsburgh Supercomputing Center through allocation CHE230105 from the Advanced Cyberinfrastructure Coordination Ecosystem: Services and Support (ACCESS) program, which is supported by National Science Foundation grant numbers 2138259, 2138286, 2138307, 2137603 and 2138296. P.W.V.B. and G.M.D. acknowledge the Iridis5 High Performance Computing facility and associated support services at the University of Southampton. Via their membership of the UK’s High End Computing Materials Chemistry Consortium, which is funded by EPSRC (grant numbers EP/R029431 and EP/X035859), this work used the UK Materials and Molecular Modelling Hub for computational resources, which is partially funded by EPSRC (grant numbers EP/T022213 and EP/W032260). Electronic structure calculations used Expanse at the San Diego Supercomputer Center through allocation number CHE160003 from the ACCESS program, which is supported by the National Science Foundation grant numbers 2138259, 2138286, 2138307, 2137603 and 2138296. A portion of this research used resources at the Spallation Neutron Source, as appropriate, a DOE Office of Science User Facility operated by the ORNL. The beam time was allocated to POWGEN and VISION on proposal number IPTS-32994.1. We thank E. Dempsey for assistance in the collection of the mass spectrometry data. Some of the work was performed in the electron microscopy core facility, which is a part of Colorado School of Mines’ Shared Instrumentation Facility (SCR_022048). Certain commercial equipment, instruments or materials are identified in this document. Such identification does not imply recommendation or endorsement by the NIST, nor does it imply that the products identified are necessarily the best available for the purpose.

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Eckstein, B. J., Martin, H. R., Moghadasnia, M. P., Halder, A., Brodale, P. S., Le Magueres, P., Butler, P. W. V., Forrest, K. A., Ritter, L., Klein, R. A., Moon, H. J., Li, C., Massimi, S. E., Cheng, Y., Hendon, C. H., Day, G. M., Space, B., Brown, C. M., & McGuirk, C. M. (Accepted/In press). A permanently porous chalcogen-bonded organic framework. Nature Synthesis. https://doi.org/10.1038/s44160-026-01072-x

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abstract = "The nature of connectivity between constituent atomic or molecular building blocks is fundamental in shaping the properties and functionality of materials. The extrapolation of emergent interatomic interactions to enable functional materials has driven transformative technological advancements. However, the bonding interactions used in material design have been largely static since the emergence of dynamic covalent chemistry \textasciitilde{}30 years ago. Here we demonstrate that non-covalent chalcogen bonding (Ch-bonding) is a distinct mode of interatomic connectivity for constructing functional materials by design. This is established by leveraging self-complementary assembly of 1,2,5-telluradiazole moieties to construct a honeycomb-type permanently porous Ch-bonded organic framework, assembled and stabilized solely through non-covalent Te···N contacts. Empirical and computational studies of electronic structure, structural healing and lattice dynamics highlight the π-type electronic communication, controlled assembly and modulated lattice dynamics in Trip3Tez-I arising directly from the unique nature of the Te···N Ch-bonding that holds substantial implications for next generation crystalline semiconductors. In addition to introducing a distinct class of permanently porous frameworks, this work establishes Ch-bonding as a programmable molecular tool for constructing functional materials with distinct properties. (Figure presented.).",

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doi = "10.1038/s44160-026-01072-x",

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AU - Martin, Hannah R.

AU - Moghadasnia, Michael P.

AU - Halder, Arijit

AU - Brodale, Parker S.

AU - Le Magueres, Pierre

AU - Butler, Patrick W.V.

AU - Forrest, Katherine A.

AU - Ritter, Logan

AU - Klein, Ryan A.

AU - Moon, Hyun June

AU - Li, Cheng

AU - Massimi, Scott E.

AU - Cheng, Yongqiang

AU - Hendon, Christopher H.

AU - Day, Graeme M.

AU - Space, Brian

AU - Brown, Craig M.

AU - McGuirk, C. Michael

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N2 - The nature of connectivity between constituent atomic or molecular building blocks is fundamental in shaping the properties and functionality of materials. The extrapolation of emergent interatomic interactions to enable functional materials has driven transformative technological advancements. However, the bonding interactions used in material design have been largely static since the emergence of dynamic covalent chemistry ~30 years ago. Here we demonstrate that non-covalent chalcogen bonding (Ch-bonding) is a distinct mode of interatomic connectivity for constructing functional materials by design. This is established by leveraging self-complementary assembly of 1,2,5-telluradiazole moieties to construct a honeycomb-type permanently porous Ch-bonded organic framework, assembled and stabilized solely through non-covalent Te···N contacts. Empirical and computational studies of electronic structure, structural healing and lattice dynamics highlight the π-type electronic communication, controlled assembly and modulated lattice dynamics in Trip3Tez-I arising directly from the unique nature of the Te···N Ch-bonding that holds substantial implications for next generation crystalline semiconductors. In addition to introducing a distinct class of permanently porous frameworks, this work establishes Ch-bonding as a programmable molecular tool for constructing functional materials with distinct properties. (Figure presented.).

AB - The nature of connectivity between constituent atomic or molecular building blocks is fundamental in shaping the properties and functionality of materials. The extrapolation of emergent interatomic interactions to enable functional materials has driven transformative technological advancements. However, the bonding interactions used in material design have been largely static since the emergence of dynamic covalent chemistry ~30 years ago. Here we demonstrate that non-covalent chalcogen bonding (Ch-bonding) is a distinct mode of interatomic connectivity for constructing functional materials by design. This is established by leveraging self-complementary assembly of 1,2,5-telluradiazole moieties to construct a honeycomb-type permanently porous Ch-bonded organic framework, assembled and stabilized solely through non-covalent Te···N contacts. Empirical and computational studies of electronic structure, structural healing and lattice dynamics highlight the π-type electronic communication, controlled assembly and modulated lattice dynamics in Trip3Tez-I arising directly from the unique nature of the Te···N Ch-bonding that holds substantial implications for next generation crystalline semiconductors. In addition to introducing a distinct class of permanently porous frameworks, this work establishes Ch-bonding as a programmable molecular tool for constructing functional materials with distinct properties. (Figure presented.).

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A permanently porous chalcogen-bonded organic framework

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