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...
| Main Authors: | , , , , |
|---|---|
| Format: | Article |
| Language: | English |
| Published: |
MDPI AG
2021-11-01
|
| Series: | Molecules |
| Subjects: | |
| Online Access: | https://www.mdpi.com/1420-3049/26/21/6731 |
| _version_ | 1797512018177032192 |
|---|---|
| author | Haruki Inoue Yuga Yamashita Yoshiki Ozawa Toshikazu Ono Masaaki Abe |
| author_facet | Haruki Inoue Yuga Yamashita Yoshiki Ozawa Toshikazu Ono Masaaki Abe |
| author_sort | Haruki Inoue |
| collection | DOAJ |
| description | 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. |
| first_indexed | 2024-03-10T05:55:02Z |
| format | Article |
| id | doaj.art-a382491b898f467ea46db5386314c4cb |
| institution | Directory Open Access Journal |
| issn | 1420-3049 |
| language | English |
| last_indexed | 2024-03-10T05:55:02Z |
| publishDate | 2021-11-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Molecules |
| spelling | doaj.art-a382491b898f467ea46db5386314c4cb2023-11-22T21:25:43ZengMDPI AGMolecules1420-30492021-11-012621673110.3390/molecules26216731Solid-State Structures and Photoluminescence of Lamellar Architectures of Cu(I) and Ag(I) Paddlewheel Clusters with Hydrogen-Bonded Polar GuestsHaruki Inoue0Yuga Yamashita1Yoshiki Ozawa2Toshikazu Ono3Masaaki Abe4Graduate School of Science, University of Hyogo, 3-2-1, Kouto, Kamigori-cho, Kobe 678-1297, JapanGraduate School of Science, University of Hyogo, 3-2-1, Kouto, Kamigori-cho, Kobe 678-1297, JapanGraduate School of Science, University of Hyogo, 3-2-1, Kouto, Kamigori-cho, Kobe 678-1297, JapanGraduate School of Engineering, Kyushu University, 744 Motooka, Nishi-ku, Fukuoka 819-0395, JapanGraduate School of Science, University of Hyogo, 3-2-1, Kouto, Kamigori-cho, Kobe 678-1297, JapanTwo 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.https://www.mdpi.com/1420-3049/26/21/6731hexanuclear paddlewheel clusterscrystal structuresphotoluminescenceguest-induced luminescence enhancementnon-covalent interactions |
| spellingShingle | Haruki Inoue Yuga Yamashita Yoshiki Ozawa Toshikazu Ono Masaaki Abe Solid-State Structures and Photoluminescence of Lamellar Architectures of Cu(I) and Ag(I) Paddlewheel Clusters with Hydrogen-Bonded Polar Guests Molecules hexanuclear paddlewheel clusters crystal structures photoluminescence guest-induced luminescence enhancement non-covalent interactions |
| title | Solid-State Structures and Photoluminescence of Lamellar Architectures of Cu(I) and Ag(I) Paddlewheel Clusters with Hydrogen-Bonded Polar Guests |
| title_full | Solid-State Structures and Photoluminescence of Lamellar Architectures of Cu(I) and Ag(I) Paddlewheel Clusters with Hydrogen-Bonded Polar Guests |
| title_fullStr | Solid-State Structures and Photoluminescence of Lamellar Architectures of Cu(I) and Ag(I) Paddlewheel Clusters with Hydrogen-Bonded Polar Guests |
| title_full_unstemmed | Solid-State Structures and Photoluminescence of Lamellar Architectures of Cu(I) and Ag(I) Paddlewheel Clusters with Hydrogen-Bonded Polar Guests |
| title_short | Solid-State Structures and Photoluminescence of Lamellar Architectures of Cu(I) and Ag(I) Paddlewheel Clusters with Hydrogen-Bonded Polar Guests |
| title_sort | solid state structures and photoluminescence of lamellar architectures of cu i and ag i paddlewheel clusters with hydrogen bonded polar guests |
| topic | hexanuclear paddlewheel clusters crystal structures photoluminescence guest-induced luminescence enhancement non-covalent interactions |
| url | https://www.mdpi.com/1420-3049/26/21/6731 |
| work_keys_str_mv | AT harukiinoue solidstatestructuresandphotoluminescenceoflamellararchitecturesofcuiandagipaddlewheelclusterswithhydrogenbondedpolarguests AT yugayamashita solidstatestructuresandphotoluminescenceoflamellararchitecturesofcuiandagipaddlewheelclusterswithhydrogenbondedpolarguests AT yoshikiozawa solidstatestructuresandphotoluminescenceoflamellararchitecturesofcuiandagipaddlewheelclusterswithhydrogenbondedpolarguests AT toshikazuono solidstatestructuresandphotoluminescenceoflamellararchitecturesofcuiandagipaddlewheelclusterswithhydrogenbondedpolarguests AT masaakiabe solidstatestructuresandphotoluminescenceoflamellararchitecturesofcuiandagipaddlewheelclusterswithhydrogenbondedpolarguests |