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Proton-switchable vapochromic behaviour of a platinum(II)-carboxy-terpyridine complex

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Please use this identifier to cite or link to this item:http://hdl.handle.net/2115/67311

Title: Proton-switchable vapochromic behaviour of a platinum(II)-carboxy-terpyridine complex
Authors: Kobayashi, Atsushi Browse this author →KAKEN DB
Oizumi, Shiori Browse this author
Shigeta, Yasuhiro Browse this author
Yoshida, Masaki Browse this author →KAKEN DB
Kato, Masako Browse this author →KAKEN DB
Issue Date: 14-Oct-2016
Publisher: Royal Society of Chemistry
Journal Title: Dalton transactions
Volume: 45
Issue: 43
Start Page: 17485
End Page: 17494
Publisher DOI: 10.1039/c6dt03189g
PMID: 27739547
Abstract: We synthesized a carboxy-substituted Pt(II)-terpyridine complex, i.e. [PtCl(Hctpy)] Cl ([1H] Cl; Hctpy = 4'-carboxy-2,2': 6',2''-terpyridine), that shows interesting switchable vapochromic behaviour upon protonation/deprotonation of the carboxy group. The as-synthesized dark-blue amorphous-like solid [1H] Cl center dot 3H(2)O was converted to a yellow crystalline solid, [1H] Cl center dot H2O, upon exposure to various polar organic solvent vapours (e.g., acetonitrile, ethanol, 1-propanol, and dichloromethane), which promote the removal of water molecules. The reaction of [1H] Cl center dot 3H(2)O with aqueous ammonia afforded a deprotonated bright-yellow crystalline complex, i.e. [PtCl(ctpy)]center dot H2O (1 center dot H2O), which exhibits red luminescence with an emission maximum at 622nm. Although the colour of 1 center dot H2O was not affected by exposure to various polar organic solvent vapours, interesting vapochromic luminescence with a remarkable red-shift of the emission maximum from 622 to 652 nm was observed upon exposure to saturated water vapour to form orange crystalline 1 center dot 3.5H(2)O X-ray structural analysis revealed that the planar and neutral complex molecule 1 forms a one-dimensional columnar structure with an intermolecular Pt center dot center dot center dot Pt distance of 3.518(2) angstrom in the orange crystall 1 center dot 3.5H(2)O, while the cationic molecule [1H](+) in the protonated form, [1H] Cl center dot H2O, generates a dimeric structure with an intermolecular Pt center dot center dot center dot Pt distance of 3.439(2) angstrom. This difference suggests that the vapochromic behaviours of the protonated and deprotonated forms could be caused by structural changes induced by water-vapour adsorption/desorption, which affect the intermolecular Pt. Pt distance, thereby changing the energy of the metal-metal-to-ligand charge-transfer (MMLCT) transition. These contrasting results for the protonated and deprotonated complexes clearly indicate that the hydrophilicity of complex 1 is significantly affected by protonation/deprotonation of the carboxy group. In addition, quasi-reversible conversion between [1H] Cl center dot 3H(2)O and 1 center dot H2O was achieved by exposure of the protonated and deprotonated forms to triethylamine and humid hydrochloric acid vapours, respectively.
Type: article (author version)
URI: http://hdl.handle.net/2115/67311
Appears in Collections:理学院・理学研究院 (Graduate School of Science / Faculty of Science) > 雑誌発表論文等 (Peer-reviewed Journal Articles, etc)

Submitter: 小林 厚志

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