Precisely Controlled Integration of Multiple Metal Cations in Diverse Metal‐Organic Framework Topologies via Messenger Building Unit Approach
Achieving precisely controlled multimetal configurations in the structure of metal‐organic frameworks (MOFs) through one‐pot reactions remains a synthetic challenge. The use of heterometallic molecular clusters as messenger building units (mBUs) is recently reported as a feasible approach to address...
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| Format: | Article |
| Language: | English |
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Wiley-VCH
2025-07-01
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| Series: | Small Structures |
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| Online Access: | https://doi.org/10.1002/sstr.202400581 |
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| author | Clara López‐García Alina A. Skorynina Fátima Esteban‐Betegón Javier Pérez‐Carvajal Marta Iglesias M. Angeles Monge Enrique Gutiérrez‐Puebla Felipe Gándara |
| author_facet | Clara López‐García Alina A. Skorynina Fátima Esteban‐Betegón Javier Pérez‐Carvajal Marta Iglesias M. Angeles Monge Enrique Gutiérrez‐Puebla Felipe Gándara |
| author_sort | Clara López‐García |
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| description | Achieving precisely controlled multimetal configurations in the structure of metal‐organic frameworks (MOFs) through one‐pot reactions remains a synthetic challenge. The use of heterometallic molecular clusters as messenger building units (mBUs) is recently reported as a feasible approach to address this issue in the formation of MOFs with sra topology. Herein, the successful expansion of this approach is reported to achieve MOFs with distinct topologies through the use of linkers with different connectivities, such as the tritopic 1,3,5‐tris(4‐carboxyphenyl)benzene (H3BTB) and the tetratopic tetrakis(4‐carboxyphenyl)porphyrin, (H6TCPP). The reaction of Ga7M mBU (M = Ni, Co) with H3BTB and H6TCPP yields porous MOFs Ga2M‐BTB and Ga7M‐TCPP, with sit and fry topology, respectively. The MOFs incorporate the initially selected metal combinations in their inorganic secondary building units, as demonstrated by the use of X‐ray diffraction, X‐ray spectroscopies, electron microscopy, and gas sorption techniques. It is also shown that alginate‐based bead shaped composites can be formed with Ga7M‐TCPP MOFs, and are efficient heterogeneous photocatalysts, as demonstrated with their use in the aza‐Henry reaction, showing improvements in activity and selectivity as compared with single‐metal analogues. |
| format | Article |
| id | doaj-art-3aa6fe43f2d24f9687c8787fa7859b1f |
| institution | Kabale University |
| issn | 2688-4062 |
| language | English |
| publishDate | 2025-07-01 |
| publisher | Wiley-VCH |
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| series | Small Structures |
| spelling | doaj-art-3aa6fe43f2d24f9687c8787fa7859b1f2025-08-20T03:28:40ZengWiley-VCHSmall Structures2688-40622025-07-0167n/an/a10.1002/sstr.202400581Precisely Controlled Integration of Multiple Metal Cations in Diverse Metal‐Organic Framework Topologies via Messenger Building Unit ApproachClara López‐García0Alina A. Skorynina1Fátima Esteban‐Betegón2Javier Pérez‐Carvajal3Marta Iglesias4M. Angeles Monge5Enrique Gutiérrez‐Puebla6Felipe Gándara7Materials Science Institute of Madrid – Spanish National Research Council (ICMM‐CSIC) Calle Sor Juana Inés de la Cruz 3 28049 Madrid SpainCELLS‐ALBA Synchrotron Carrer de la Llum 2‐26, Cerdanyola del Vallès 08290 Barcelona SpainMaterials Science Institute of Madrid – Spanish National Research Council (ICMM‐CSIC) Calle Sor Juana Inés de la Cruz 3 28049 Madrid SpainMaterials Science Institute of Madrid – Spanish National Research Council (ICMM‐CSIC) Calle Sor Juana Inés de la Cruz 3 28049 Madrid SpainMaterials Science Institute of Madrid – Spanish National Research Council (ICMM‐CSIC) Calle Sor Juana Inés de la Cruz 3 28049 Madrid SpainMaterials Science Institute of Madrid – Spanish National Research Council (ICMM‐CSIC) Calle Sor Juana Inés de la Cruz 3 28049 Madrid SpainMaterials Science Institute of Madrid – Spanish National Research Council (ICMM‐CSIC) Calle Sor Juana Inés de la Cruz 3 28049 Madrid SpainMaterials Science Institute of Madrid – Spanish National Research Council (ICMM‐CSIC) Calle Sor Juana Inés de la Cruz 3 28049 Madrid SpainAchieving precisely controlled multimetal configurations in the structure of metal‐organic frameworks (MOFs) through one‐pot reactions remains a synthetic challenge. The use of heterometallic molecular clusters as messenger building units (mBUs) is recently reported as a feasible approach to address this issue in the formation of MOFs with sra topology. Herein, the successful expansion of this approach is reported to achieve MOFs with distinct topologies through the use of linkers with different connectivities, such as the tritopic 1,3,5‐tris(4‐carboxyphenyl)benzene (H3BTB) and the tetratopic tetrakis(4‐carboxyphenyl)porphyrin, (H6TCPP). The reaction of Ga7M mBU (M = Ni, Co) with H3BTB and H6TCPP yields porous MOFs Ga2M‐BTB and Ga7M‐TCPP, with sit and fry topology, respectively. The MOFs incorporate the initially selected metal combinations in their inorganic secondary building units, as demonstrated by the use of X‐ray diffraction, X‐ray spectroscopies, electron microscopy, and gas sorption techniques. It is also shown that alginate‐based bead shaped composites can be formed with Ga7M‐TCPP MOFs, and are efficient heterogeneous photocatalysts, as demonstrated with their use in the aza‐Henry reaction, showing improvements in activity and selectivity as compared with single‐metal analogues.https://doi.org/10.1002/sstr.202400581messenger building unitsmetal‐organic frameworksmultimetalsphotocatalysis |
| spellingShingle | Clara López‐García Alina A. Skorynina Fátima Esteban‐Betegón Javier Pérez‐Carvajal Marta Iglesias M. Angeles Monge Enrique Gutiérrez‐Puebla Felipe Gándara Precisely Controlled Integration of Multiple Metal Cations in Diverse Metal‐Organic Framework Topologies via Messenger Building Unit Approach Small Structures messenger building units metal‐organic frameworks multimetals photocatalysis |
| title | Precisely Controlled Integration of Multiple Metal Cations in Diverse Metal‐Organic Framework Topologies via Messenger Building Unit Approach |
| title_full | Precisely Controlled Integration of Multiple Metal Cations in Diverse Metal‐Organic Framework Topologies via Messenger Building Unit Approach |
| title_fullStr | Precisely Controlled Integration of Multiple Metal Cations in Diverse Metal‐Organic Framework Topologies via Messenger Building Unit Approach |
| title_full_unstemmed | Precisely Controlled Integration of Multiple Metal Cations in Diverse Metal‐Organic Framework Topologies via Messenger Building Unit Approach |
| title_short | Precisely Controlled Integration of Multiple Metal Cations in Diverse Metal‐Organic Framework Topologies via Messenger Building Unit Approach |
| title_sort | precisely controlled integration of multiple metal cations in diverse metal organic framework topologies via messenger building unit approach |
| topic | messenger building units metal‐organic frameworks multimetals photocatalysis |
| url | https://doi.org/10.1002/sstr.202400581 |
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