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: [Cu6(Hmna)6]·7DMF (1·7DMF) and [Ag6(Hmna)6]·8...

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Autores principales:	Haruki Inoue, Yuga Yamashita, Yoshiki Ozawa, Toshikazu Ono, Masaaki Abe
Formato:	article
Lenguaje:	EN
Publicado:	MDPI AG 2021
Materias:	hexanuclear paddlewheel clusters crystal structures photoluminescence guest-induced luminescence enhancement non-covalent interactions Organic chemistry QD241-441
Acceso en línea:	https://doaj.org/article/a382491b898f467ea46db5386314c4cb
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spelling	oai:doaj.org-article:a382491b898f467ea46db5386314c4cb2021-11-11T18:40:05ZSolid-State Structures and Photoluminescence of Lamellar Architectures of Cu(I) and Ag(I) Paddlewheel Clusters with Hydrogen-Bonded Polar Guests10.3390/molecules262167311420-3049https://doaj.org/article/a382491b898f467ea46db5386314c4cb2021-11-01T00:00:00Zhttps://www.mdpi.com/1420-3049/26/21/6731https://doaj.org/toc/1420-3049Two 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.Haruki InoueYuga YamashitaYoshiki OzawaToshikazu OnoMasaaki AbeMDPI AGarticlehexanuclear paddlewheel clusterscrystal structuresphotoluminescenceguest-induced luminescence enhancementnon-covalent interactionsOrganic chemistryQD241-441ENMolecules, Vol 26, Iss 6731, p 6731 (2021)
institution	DOAJ
collection	DOAJ
language	EN
topic	hexanuclear paddlewheel clusters crystal structures photoluminescence guest-induced luminescence enhancement non-covalent interactions Organic chemistry QD241-441
spellingShingle	hexanuclear paddlewheel clusters crystal structures photoluminescence guest-induced luminescence enhancement non-covalent interactions Organic chemistry QD241-441 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
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.
format	article
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
title	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_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_sort	solid-state structures and photoluminescence of lamellar architectures of cu(i) and ag(i) paddlewheel clusters with hydrogen-bonded polar guests
publisher	MDPI AG
publishDate	2021
url	https://doaj.org/article/a382491b898f467ea46db5386314c4cb
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Solid-State Structures and Photoluminescence of Lamellar Architectures of Cu(I) and Ag(I) Paddlewheel Clusters with Hydrogen-Bonded Polar Guests

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