Phenol-Driven Modulation Enables the Crystallization of Titanium Metal–Organic Frameworks
Abstract Titanium-based metal–organic frameworks (MOFs) remain among the most challenging frameworks to synthesize due to the high reactivity of Ti(IV) precursors, particularly when in combination with strongly coordinating phenolate ligands. Phenol is an untapped modulator for MOF synthesis that enabled the formation of a new crystalline Ti-MOF phase, otherwise unattainable through established modulators. We show how transient Ti-phenolate species formed in solution regulate titanium coordination equilibria and demonstrate the broader applicability of phenol modulation for several reported Ti-MOF systems. As a result of phenol modulation, we isolate a previously elusive crystalline titanium ellagate sustainable MOF, TUW-11, composed of monometallic Ti(IV) centers and plant-derived ellagic acid linkers. Three-dimensional electron diffraction, synchrotron X-ray techniques, and scanning transmission electron microscopy reveal a layered microporous framework with 1.1 nm channels. TUW-11 exhibits a narrow band gap, p-type semiconducting behavior, and ligand-centered visible-light photoresponse. These findings demonstrate phenol modulation as a powerful strategy for controlling titanium-phenolate framework formation and expand the synthetic toolbox available for Ti-MOF discovery.
Authors
- Dominik Eder (ORCID: https://orcid.org/0000-0002-5395-564X)
- Freddy Kleitz (ORCID: https://orcid.org/0000-0001-6769-4180)
- Georg Gescheidt (ORCID: https://orcid.org/0000-0002-6827-4337)
- Florian Libisch (ORCID: https://orcid.org/0000-0001-5641-9458)
- Alexey S. Cherevan (ORCID: https://orcid.org/0000-0001-8934-6371)
- Tom Willhammar (ORCID: https://orcid.org/0000-0001-6120-1218)
- Zheao Huang (ORCID: https://orcid.org/0000-0002-4715-4598)
- Cornelia von Baeckmann (ORCID: https://orcid.org/0000-0002-2337-9063)
- Natalia M. Padial (ORCID: https://orcid.org/0000-0001-6067-3360)
- Max Schmallegger (ORCID: https://orcid.org/0000-0001-6097-8252)
- A. Ken Inge (ORCID: https://orcid.org/0000-0001-9118-1342)
- Pablo Ayala (ORCID: https://orcid.org/0000-0002-2569-4438)
- Doğukan Hazar Apaydın (ORCID: https://orcid.org/0000-0002-1075-8857)
- Carlos Martí‐Gastaldo (ORCID: https://orcid.org/0000-0003-3203-0047)
- Magdalena Ladisich (ORCID: https://orcid.org/0009-0006-6678-8189)
- Guillermo Gómez-Tenés (ORCID: https://orcid.org/0000-0001-7062-7974)
- Maria Asghar
- Sarah Hermetinger
- Yan Zheng
- Yu Xia
Institutions
- University of Vienna (AT)
- TU Wien (AT)
- Universitat de València (ES)
- Stockholm University (SE)
- Graz University of Technology (AT)
Publication Details
- Journal
- Journal of the American Chemical Society
- Published
- 2026-10-29
- DOI
- https://doi.org/10.1021/jacs.6c16169
- Primary Topic
- Metal-Organic Frameworks: Synthesis and Applications
- Type
- article
- Field-Weighted Citation Impact
- 0.00
Funders
- Technische Universitat Wien
- European Commission
- European Synchrotron Radiation Facility
- Svenska Forskningsrådet Formas
- Austrian Science Fund
- Carl Tryggers Stiftelse för Vetenskaplig Forskning
- Universität Wien
- Knut och Alice Wallenbergs Stiftelse
- Vetenskapsrådet
- Technische Universität Wien
- Horizon 2020 Framework Programme
- HORIZON EUROPE Framework Programme
- Agencia Estatal de Investigación
- European Social Fund