A Fused Poly(truncated rhombic dodecahedron)-Containing 3D Coordination Polymer: A Multifunctional Material with Exceptional Properties
| Autor: | Adrien Schlachter, Michael Knorr, Pierre D. Harvey, Rebecca Scheel, Kevin Tanner, Carsten Strohmann, Paul-Ludovic Karsenti |
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| Přispěvatelé: | Département de chimie [Sherbrooke] (UdeS), Faculté des sciences [Sherbrooke] (UdeS), Université de Sherbrooke (UdeS)-Université de Sherbrooke (UdeS), Technische Universität Dortmund [Dortmund] (TU), Univers, Transport, Interfaces, Nanostructures, Atmosphère et environnement, Molécules (UMR 6213) (UTINAM), Institut national des sciences de l'Univers (INSU - CNRS)-Centre National de la Recherche Scientifique (CNRS)-Université de Franche-Comté (UFC), Université Bourgogne Franche-Comté [COMUE] (UBFC)-Université Bourgogne Franche-Comté [COMUE] (UBFC) |
| Jazyk: | angličtina |
| Rok vydání: | 2021 |
| Předmět: |
Thermochromism
010405 organic chemistry Coordination polymer Ligand Excited states 010402 general chemistry Ligands 01 natural sciences 0104 chemical sciences Inorganic Chemistry Rhombic dodecahedron Coordination polymers chemistry.chemical_compound Crystallography chemistry Cubane Excited state [CHIM]Chemical Sciences Singlet state Physical and Theoretical Chemistry Phosphorescence Diffraction Materials |
| Zdroj: | Inorganic Chemistry Inorganic Chemistry, American Chemical Society, In press, ⟨10.1021/acs.inorgchem.1c01856⟩ |
| ISSN: | 0020-1669 1520-510X |
| Popis: | International audience; The design of new and inexpensive metal-containing functional materials is of great interest. Herein is reported a unique thermochromic near-IR emitting coordination polymer, 3D-[Cu8I8(L1)2]n, CP2, which is formed when ArS(CH2)4SAr (L1, Ar = 4-C6H4OMe) reacts with 2 equiv of CuI in EtCN. In MeCN, CP1 ([Cu4I4(L1)(MeCN)2]n, consisting of an alternating [-Cu4I4-L1-Cu4I4-L1-]n chain where the Cu4I4 cubane units bear two metal-bound MeCN molecules, is formed. Heat-driven elimination of these MeCN’s in solid CP1 also leads to CP2 through a predisposed organization of the Cu4I4 units prone to fusion after MeCN eliminations (i.e., a rare case of template effect). The CP2 structure exhibits parallel 1D-(Cu8I8)n chains, (z-axis; designated 1D-[CuI]n) as secondary building units (SBU) held together by parallel thioether ligands (x,y-axes), forming a nonporous 3D network. The structure of this 1D-[CuI]n SBU is unprecedented and consists of a series of fused and twisted open Cu4I4 cubanes forming a fused poly(truncated rhombic dodecahedron). Unexpectedly, the compact 3D CP2 exhibits a solid-to-solid phase transition at 100 °C and a hysteresis of ∼20 °C. CP1 emits intensively (298 K: λemi = 564 nm; Φe = 0.35), whereas CP2 presents a strongly red-shifted weaker emission (298 K: λemi ∼ 740 nm, Φe < 0.0001). Moreover, CP2, which is stable over long periods of time, exhibits thermochromism where the emission intensity of the near-IR band decreases significantly at the benefit of a ligand-centered phosphorescence at 415 nm. Altogether, these properties listed above make CP2 exceptional. The low-energy singlet and triplet excited states have been assigned to ligand/metal-to-ligand charge transfer based on DFT and TD-DFT computations. |
| Databáze: | OpenAIRE |
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