A Permanently Porous Chalcogen-Bonded Organic Framework

Eckstein, Brian [Colorado School of Mines]; Martin, Hannah [Colorado School of Mines]; Moghadasnia, Michael [Colorado School of Mines]; Halder, Arijit [Colorado School of Mines]; Brodale, Parker [University of Oregon]; Le Magueres, Pierre [Rigaku Corporation]; Butler, Patrick [University of Southampton]; Forrest, Katherine [North Carolina State University]; Ritter, Logan [North Carolina State University]; Klein, Ryan [National Laboratory of the Rockies, Golden, CO (United States)] (ORCID:0000000268076701); Moon, Hyun [United States Department of Commerce; University of Delaware]; Li, Cheng [Oak Ridge National Laboratory]; Massimi, Scott [Colorado School of Mines]; Cheng, Yongqiang [Oak Ridge National Laboratory]; Hendon, Christopher [University of Oregon]; Day, Graeme [University of Southampton]; Space, Brian [North Carolina State University]; Brown, Craig [United States Department of Commerce; University of Delaware]; McGuirk, C. Michael [Colorado School of Mines]

doi:10.1038/s44160-026-01072-x

DOE OSTI · 3367504

A Permanently Porous Chalcogen-Bonded Organic Framework

Eckstein, Brian [Colorado School of Mines]·Martin, Hannah [Colorado School of Mines]·Moghadasnia, Michael [Colorado School of Mines]·Halder, Arijit [Colorado School of Mines]·Brodale, Parker [University of Oregon]·Le Magueres, Pierre [Rigaku Corporation]·Butler, Patrick [University of Southampton]·Forrest, Katherine [North Carolina State University]·Ritter, Logan [North Carolina State University]·Klein, Ryan [National Laboratory of the Rockies, Golden, CO (United States)] (ORCID:0000000268076701)·Moon, Hyun [United States Department of Commerce; University of Delaware]·Li, Cheng [Oak Ridge National Laboratory]·Massimi, Scott [Colorado School of Mines]·Cheng, Yongqiang [Oak Ridge National Laboratory]·Hendon, Christopher [University of Oregon]·Day, Graeme [University of Southampton]·Space, Brian [North Carolina State University]·Brown, Craig [United States Department of Commerce; University of Delaware]·McGuirk, C. Michael [Colorado School of Mines]

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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 ~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 pi-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.

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY Ch-bonding non-covalent chalcogen bonding permanently porous frameworks

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Eckstein, Brian [Colorado School of Mines], Martin, Hannah [Colorado School of Mines], Moghadasnia, Michael [Colorado School of Mines], Halder, Arijit [Colorado School of Mines], Brodale, Parker [University of Oregon], Le Magueres, Pierre [Rigaku Corporation], Butler, Patrick [University of Southampton], Forrest, Katherine [North Carolina State University], Ritter, Logan [North Carolina State University], Klein, Ryan [National Laboratory of the Rockies, Golden, CO (United States)] (ORCID:0000000268076701), Moon, Hyun [United States Department of Commerce; University of Delaware], Li, Cheng [Oak Ridge National Laboratory], Massimi, Scott [Colorado School of Mines], Cheng, Yongqiang [Oak Ridge National Laboratory], Hendon, Christopher [University of Oregon], Day, Graeme [University of Southampton], Space, Brian [North Carolina State University], Brown, Craig [United States Department of Commerce; University of Delaware], McGuirk, C. Michael [Colorado School of Mines]. 2026-05-15. A Permanently Porous Chalcogen-Bonded Organic Framework. https://doi.org/10.1038/s44160-026-01072-x

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY subject Ch-bonding subject non-covalent chalcogen bonding subject permanently porous frameworks subject

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