Photo-controlled vacancies and conductivity within single crystals of silver chalcogenolate cluster-based MOFs
Abstract Structural vacancies in crystalline solids have great potential in tuning optoelectronic properties for specific applications. However, the random distribution of vacancies is still an intractable problem when creating materials with completely reproducible functions. Here, we report that t...
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Nature Portfolio
2025-07-01
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| Series: | Nature Communications |
| Online Access: | https://doi.org/10.1038/s41467-025-60720-6 |
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| author | Kai Ma Xue-Mei Liu Xi-Yan Dong Xi-Ming Luo Hai-Yang Li Shuang-Quan Zang Thomas C. W. Mak |
| author_facet | Kai Ma Xue-Mei Liu Xi-Yan Dong Xi-Ming Luo Hai-Yang Li Shuang-Quan Zang Thomas C. W. Mak |
| author_sort | Kai Ma |
| collection | DOAJ |
| description | Abstract Structural vacancies in crystalline solids have great potential in tuning optoelectronic properties for specific applications. However, the random distribution of vacancies is still an intractable problem when creating materials with completely reproducible functions. Here, we report that the growth of crystals from solution approaching perfect single crystallization of assembled silver clusters (SC-1, where SC denotes single crystal), featuring a two-dimensional (2D)-three-dimensional (3D) interpenetrating conformation. By controlling the ultraviolet (UV) irradiation time, SC-1 transformed into SC-2-0.8 and then into SC-2-0.5, where partial trifluoroacetic acid (TFA) and the linker molecules (1,2,4,5-tetracyanobenzene, termed TCNB) possessed a 0.8 or 0.5 occupancy in the crystallography, forming ordered vacancies at specific sites. This course led to a deepened color, a diminished photoluminescence, a narrowed energy gap, and an average 50-fold increase in the single-crystal electron conductivity, together with a 3D-3D interpenetrating conformation. Over time, under the original conditions, SC-1 regrew into SC-3, which had a 3D noninterpenetrating conformation with no crystallographic vacancies and a conductivity similar to that of SC-1. This work elucidates the correlation between the tunable vacancy number and electrical conductivity at the atomic level, providing a method for facilitating electronic communication between cluster-building units and creating ordered-vacancy conducting materials. |
| format | Article |
| id | doaj-art-2d543c1e897e42c49e5341bb52782498 |
| institution | DOAJ |
| issn | 2041-1723 |
| language | English |
| publishDate | 2025-07-01 |
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| spelling | doaj-art-2d543c1e897e42c49e5341bb527824982025-08-20T03:03:37ZengNature PortfolioNature Communications2041-17232025-07-0116111010.1038/s41467-025-60720-6Photo-controlled vacancies and conductivity within single crystals of silver chalcogenolate cluster-based MOFsKai Ma0Xue-Mei Liu1Xi-Yan Dong2Xi-Ming Luo3Hai-Yang Li4Shuang-Quan Zang5Thomas C. W. Mak6College of Chemistry, Zhengzhou UniversityCollege of Chemistry, Zhengzhou UniversityCollege of Chemistry, Zhengzhou UniversityCollege of Chemistry, Zhengzhou UniversityCollege of Chemistry, Zhengzhou UniversityCollege of Chemistry, Zhengzhou UniversityCollege of Chemistry, Zhengzhou UniversityAbstract Structural vacancies in crystalline solids have great potential in tuning optoelectronic properties for specific applications. However, the random distribution of vacancies is still an intractable problem when creating materials with completely reproducible functions. Here, we report that the growth of crystals from solution approaching perfect single crystallization of assembled silver clusters (SC-1, where SC denotes single crystal), featuring a two-dimensional (2D)-three-dimensional (3D) interpenetrating conformation. By controlling the ultraviolet (UV) irradiation time, SC-1 transformed into SC-2-0.8 and then into SC-2-0.5, where partial trifluoroacetic acid (TFA) and the linker molecules (1,2,4,5-tetracyanobenzene, termed TCNB) possessed a 0.8 or 0.5 occupancy in the crystallography, forming ordered vacancies at specific sites. This course led to a deepened color, a diminished photoluminescence, a narrowed energy gap, and an average 50-fold increase in the single-crystal electron conductivity, together with a 3D-3D interpenetrating conformation. Over time, under the original conditions, SC-1 regrew into SC-3, which had a 3D noninterpenetrating conformation with no crystallographic vacancies and a conductivity similar to that of SC-1. This work elucidates the correlation between the tunable vacancy number and electrical conductivity at the atomic level, providing a method for facilitating electronic communication between cluster-building units and creating ordered-vacancy conducting materials.https://doi.org/10.1038/s41467-025-60720-6 |
| spellingShingle | Kai Ma Xue-Mei Liu Xi-Yan Dong Xi-Ming Luo Hai-Yang Li Shuang-Quan Zang Thomas C. W. Mak Photo-controlled vacancies and conductivity within single crystals of silver chalcogenolate cluster-based MOFs Nature Communications |
| title | Photo-controlled vacancies and conductivity within single crystals of silver chalcogenolate cluster-based MOFs |
| title_full | Photo-controlled vacancies and conductivity within single crystals of silver chalcogenolate cluster-based MOFs |
| title_fullStr | Photo-controlled vacancies and conductivity within single crystals of silver chalcogenolate cluster-based MOFs |
| title_full_unstemmed | Photo-controlled vacancies and conductivity within single crystals of silver chalcogenolate cluster-based MOFs |
| title_short | Photo-controlled vacancies and conductivity within single crystals of silver chalcogenolate cluster-based MOFs |
| title_sort | photo controlled vacancies and conductivity within single crystals of silver chalcogenolate cluster based mofs |
| url | https://doi.org/10.1038/s41467-025-60720-6 |
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