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Inducing Reactivity by Cluster Strain in Titanium Frameworks.

Eloy P Gómez-Oliveira1, Vitor Fernandes de Almeida2, Javier Castells-Gil3

  • 1Functional Inorganic Materials Team, Instituto de Ciencia Molecular (ICMol), Universitat de València, 46980 València, Spain.

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|December 24, 2025
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Summary
This summary is machine-generated.

We demonstrate cluster strain engineering in titanium-organic frameworks by substituting cations. This method predictably distorts metal-oxo clusters, enhancing redox activity for applications like photocatalytic CO2 methanation.

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Area of Science:

  • Materials Science
  • Chemistry
  • Catalysis

Background:

  • Strategies for distorting metal-oxo clusters in molecular frameworks are limited.
  • Controlling charge separation and redox activity in frameworks is crucial.

Purpose of the Study:

  • To present a proof-of-concept for cluster strain engineering in titanium-organic frameworks.
  • To investigate the effect of cation substitution on cluster distortion and redox properties.

Main Methods:

  • Utilized MUV-10 (a titanium-organic framework) as a model system.
  • Replaced Ca2+ with larger alkaline-earth cations (Sr2+, Ba2+) to induce strain.
  • Analyzed structural changes and photocatalytic activity (CO2 methanation).

Main Results:

  • Achieved predictable distortions of Ti2M2 clusters and a cubic-to-tetragonal cell transformation.
  • Observed altered Ti-O coordination geometry and enhanced ligand-to-metal charge transfer.
  • Promoted photogeneration of Ti3+ sites, validated by photocatalytic CO2 methanation.

Conclusions:

  • Established cluster strain engineering as a method to modulate redox reactivity in molecular solids.
  • Linked oxide catalysis and reticular chemistry through cluster strain.
  • Repurposed the Goldschmidt tolerance factor to rationalize strain in reticular frameworks.