Solid-State Structures and Photoluminescence of Lamellar Architectures of Cu(I) and Ag(I) Paddlewheel Clusters with Hydrogen-Bonded Polar Guests
Two hexanuclear paddlewheel-like clusters appending six carboxylic-acid pendants have been isolated with the inclusion of polar solvent guests: [Cu<sub>6</sub>(Hmna)<sub>6</sub>]·7DMF (<b>1</b>·7DMF) and [Ag<sub>6</sub>(Hmna)<sub>6</sub>]·8...
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| Autores principales: | , , , , |
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| Formato: | article |
| Lenguaje: | EN |
| Publicado: |
MDPI AG
2021
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| Materias: | |
| Acceso en línea: | https://doaj.org/article/a382491b898f467ea46db5386314c4cb |
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| Sumario: | Two hexanuclear paddlewheel-like clusters appending six carboxylic-acid pendants have been isolated with the inclusion of polar solvent guests: [Cu<sub>6</sub>(Hmna)<sub>6</sub>]·7DMF (<b>1</b>·7DMF) and [Ag<sub>6</sub>(Hmna)<sub>6</sub>]·8DMSO (<b>2</b>·8DMSO), where H<sub>2</sub>mna = 2-mercaptonicotininc acid, DMF = <i>N</i>,<i>N</i>’-dimethylformamide, and DMSO = dimethyl sulfoxide. The solvated clusters, together with their fully desolvated forms <b>1</b> and <b>2</b>, have been characterized by FTIR, UV–Vis diffuse reflectance spectroscopy, TG-DTA analysis, and DFT calculations. Crystal structures of two solvated clusters <b>1</b>·7DMF and <b>2</b>·8DMSO have been unambiguously determined by single-crystal X-ray diffraction analysis. Six carboxylic groups appended on the clusters trap solvent guests, DMF or DMSO, through H-bonds. As a result, alternately stacked lamellar architectures comprising of a paddlewheel cluster layer and H-bonded solvent layer are formed. Upon UV illumination (<i>λ</i><sub>ex</sub> = 365 nm), the solvated hexasilver(I) cluster <b>2</b>·8DMSO gives intense greenish-yellow photoluminescence in the solid state (<i>λ</i><sub>PL</sub> = 545 nm, <i>Φ</i><sub>PL</sub> = 0.17 at 298 K), whereas the solvated hexacopper(I) cluster <b>1</b>·7DMF displays PL in the near-IR region (<i>λ</i><sub>PL</sub> = 765 nm, <i>Φ</i><sub>PL</sub> = 0.38 at 298 K). Upon complete desolvation, a substantial bleach in the PL intensity (<i>Φ</i><sub>PL</sub> < 0.01) is observed. The desorption–sorption response was studied by the solid-state PL spectroscopy. Non-covalent interactions in the crystal including intermolecular H-bonds, CH⋯π interactions, and π⋯π stack were found to play decisive roles in the creation of the lamellar architectures, small-molecule trap-and-release behavior, and guest-induced luminescence enhancement. |
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