Excited‐State Structural Dynamics of the Cubane‐Type Metal Cluster [Cu4I4(py)4] Explored by Time‐Resolved X‐Ray Liquidography
Abstract Cubane‐type metal clusters respond uniquely to stimuli like light and electric potential, resulting in behaviors such as crystal‐to‐crystal phase transitions. While structural adaptability is known to be linked to these responses, direct experimental evidence for the associated structural c...
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Wiley
2025-04-01
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| Series: | Advanced Science |
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| Online Access: | https://doi.org/10.1002/advs.202414970 |
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| author | Doyeong Kim Hosung Ki Donghwan Im Yunbeom Lee Seonggon Lee Jun Heo Seunghwan Eom Eun Hyuk Choi Doo‐Sik Ahn Hyotcherl Ihee |
| author_facet | Doyeong Kim Hosung Ki Donghwan Im Yunbeom Lee Seonggon Lee Jun Heo Seunghwan Eom Eun Hyuk Choi Doo‐Sik Ahn Hyotcherl Ihee |
| author_sort | Doyeong Kim |
| collection | DOAJ |
| description | Abstract Cubane‐type metal clusters respond uniquely to stimuli like light and electric potential, resulting in behaviors such as crystal‐to‐crystal phase transitions. While structural adaptability is known to be linked to these responses, direct experimental evidence for the associated structural changes has been missing. This study addresses this gap by examining the structural dynamics of the copper(I) iodide cubane (Cu4I4(py)4, py = pyridine) upon photoexcitation using time‐resolved X‐ray liquidography. The results reveal: 1) 100 picoseconds (ps) after excitation, two distinct excited states—the cluster‐centered triplet (3CC) state and the (metal+halide)‐to‐ligand charge transfer triplet (3(M/X)LCT) state—are present; 2) the 3(M/X)LCT state decays with an apparent time constant of 1.21 ns, primarily transitioning to the 3CC state, with a small fraction undergoing decay to the ground state (GS); and 3) the 3CC state eventually returns to the GS. The molecular structures, provided for these states serve as benchmarks for theoretical studies. Importantly, the 3CC structure exhibits significant distortion in the Cu4I4 core and reduced symmetry, findings that are unanticipated by previous models. This comprehensive investigation deepens the understanding of the structural transformations occurring upon photoexcitation, with a potential impact on future applications of these compounds as versatile components in photosensitive metal–organic frameworks. |
| format | Article |
| id | doaj-art-cbcea0ed262541b98a7c5dd5f48a9b35 |
| institution | OA Journals |
| issn | 2198-3844 |
| language | English |
| publishDate | 2025-04-01 |
| publisher | Wiley |
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| series | Advanced Science |
| spelling | doaj-art-cbcea0ed262541b98a7c5dd5f48a9b352025-08-20T02:16:22ZengWileyAdvanced Science2198-38442025-04-011214n/an/a10.1002/advs.202414970Excited‐State Structural Dynamics of the Cubane‐Type Metal Cluster [Cu4I4(py)4] Explored by Time‐Resolved X‐Ray LiquidographyDoyeong Kim0Hosung Ki1Donghwan Im2Yunbeom Lee3Seonggon Lee4Jun Heo5Seunghwan Eom6Eun Hyuk Choi7Doo‐Sik Ahn8Hyotcherl Ihee9Department of Chemistry Korea Advanced Institute of Science and Technology (KAIST) Daejeon 34141 Republic of KoreaDepartment of Chemistry Korea Advanced Institute of Science and Technology (KAIST) Daejeon 34141 Republic of KoreaDepartment of Chemistry Korea Advanced Institute of Science and Technology (KAIST) Daejeon 34141 Republic of KoreaDepartment of Chemistry Korea Advanced Institute of Science and Technology (KAIST) Daejeon 34141 Republic of KoreaDepartment of Chemistry Korea Advanced Institute of Science and Technology (KAIST) Daejeon 34141 Republic of KoreaCenter for Advanced Reaction Dynamics Institute for Basic Science (IBS) Daejeon 34141 Republic of KoreaDepartment of Chemistry Korea Advanced Institute of Science and Technology (KAIST) Daejeon 34141 Republic of KoreaDepartment of Chemistry Korea Advanced Institute of Science and Technology (KAIST) Daejeon 34141 Republic of KoreaCenter for Advanced Reaction Dynamics Institute for Basic Science (IBS) Daejeon 34141 Republic of KoreaDepartment of Chemistry Korea Advanced Institute of Science and Technology (KAIST) Daejeon 34141 Republic of KoreaAbstract Cubane‐type metal clusters respond uniquely to stimuli like light and electric potential, resulting in behaviors such as crystal‐to‐crystal phase transitions. While structural adaptability is known to be linked to these responses, direct experimental evidence for the associated structural changes has been missing. This study addresses this gap by examining the structural dynamics of the copper(I) iodide cubane (Cu4I4(py)4, py = pyridine) upon photoexcitation using time‐resolved X‐ray liquidography. The results reveal: 1) 100 picoseconds (ps) after excitation, two distinct excited states—the cluster‐centered triplet (3CC) state and the (metal+halide)‐to‐ligand charge transfer triplet (3(M/X)LCT) state—are present; 2) the 3(M/X)LCT state decays with an apparent time constant of 1.21 ns, primarily transitioning to the 3CC state, with a small fraction undergoing decay to the ground state (GS); and 3) the 3CC state eventually returns to the GS. The molecular structures, provided for these states serve as benchmarks for theoretical studies. Importantly, the 3CC structure exhibits significant distortion in the Cu4I4 core and reduced symmetry, findings that are unanticipated by previous models. This comprehensive investigation deepens the understanding of the structural transformations occurring upon photoexcitation, with a potential impact on future applications of these compounds as versatile components in photosensitive metal–organic frameworks.https://doi.org/10.1002/advs.202414970cubane‐type metal clustermolecular structural dynamicsreaction dynamicstime‐resolved X‐ray liquidographytime‐resolved X‐ray solution scattering |
| spellingShingle | Doyeong Kim Hosung Ki Donghwan Im Yunbeom Lee Seonggon Lee Jun Heo Seunghwan Eom Eun Hyuk Choi Doo‐Sik Ahn Hyotcherl Ihee Excited‐State Structural Dynamics of the Cubane‐Type Metal Cluster [Cu4I4(py)4] Explored by Time‐Resolved X‐Ray Liquidography Advanced Science cubane‐type metal cluster molecular structural dynamics reaction dynamics time‐resolved X‐ray liquidography time‐resolved X‐ray solution scattering |
| title | Excited‐State Structural Dynamics of the Cubane‐Type Metal Cluster [Cu4I4(py)4] Explored by Time‐Resolved X‐Ray Liquidography |
| title_full | Excited‐State Structural Dynamics of the Cubane‐Type Metal Cluster [Cu4I4(py)4] Explored by Time‐Resolved X‐Ray Liquidography |
| title_fullStr | Excited‐State Structural Dynamics of the Cubane‐Type Metal Cluster [Cu4I4(py)4] Explored by Time‐Resolved X‐Ray Liquidography |
| title_full_unstemmed | Excited‐State Structural Dynamics of the Cubane‐Type Metal Cluster [Cu4I4(py)4] Explored by Time‐Resolved X‐Ray Liquidography |
| title_short | Excited‐State Structural Dynamics of the Cubane‐Type Metal Cluster [Cu4I4(py)4] Explored by Time‐Resolved X‐Ray Liquidography |
| title_sort | excited state structural dynamics of the cubane type metal cluster cu4i4 py 4 explored by time resolved x ray liquidography |
| topic | cubane‐type metal cluster molecular structural dynamics reaction dynamics time‐resolved X‐ray liquidography time‐resolved X‐ray solution scattering |
| url | https://doi.org/10.1002/advs.202414970 |
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