High Pressure Spectroscopic Investigation on Proton Transfer in Squaric Acid and 4,4′-Bipyridine Co-crystal

Abstract In attempt to the obtain detailed geometric information of proton transfer compound (subsequently denote as SQBP) formed between squaric acid (SQ)and 4,4′-bipyridine(BP), and to investigate the mechanisms of pressure-induced double proton transfer and related structural phase transition, we...

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Autores principales:	Zhiwei Ma, Juntao Li, Chunyu Liu, Chenglin Sun, Mi Zhou
Formato:	article
Lenguaje:	EN
Publicado:	Nature Portfolio 2017
Materias:	Medicine R Science Q
Acceso en línea:	https://doaj.org/article/1ba6618b27b042788053850c96948bb9
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spelling	oai:doaj.org-article:1ba6618b27b042788053850c96948bb92021-12-02T12:30:12ZHigh Pressure Spectroscopic Investigation on Proton Transfer in Squaric Acid and 4,4′-Bipyridine Co-crystal10.1038/s41598-017-04980-32045-2322https://doaj.org/article/1ba6618b27b042788053850c96948bb92017-07-01T00:00:00Zhttps://doi.org/10.1038/s41598-017-04980-3https://doaj.org/toc/2045-2322Abstract In attempt to the obtain detailed geometric information of proton transfer compound (subsequently denote as SQBP) formed between squaric acid (SQ)and 4,4′-bipyridine(BP), and to investigate the mechanisms of pressure-induced double proton transfer and related structural phase transition, we carried out in-situ high pressure Raman spectroscopy of SQBP up to 20 GPa. A solid-solid phase transition together with double proton transfer phenomenon was confirmed by Raman spectroscopy at about 1.5 GPa, and the activation of C = O stretching mode in Raman spectra indicates a square-ring structure of SQ with four symmetric C = O bond formation. These results are further supported by first-principals calculations and in-situ high pressure infrared absorption spectroscopy. Additionally, Raman intensity analysis suggests that a higher-order phase transition with planar BP molecular structure occurred in the pressure range of 3~6 GPa. As a result, the π electron delocalization effect in BP dominated the intensity enhancement of C = O stretching mode in SQ. To the best of our knowledge, this is the first time observation of the intensity enhancement of proton donor’s normal modes induced by proton acceptor’s π electron delocalization.Zhiwei MaJuntao LiChunyu LiuChenglin SunMi ZhouNature PortfolioarticleMedicineRScienceQENScientific Reports, Vol 7, Iss 1, Pp 1-8 (2017)
institution	DOAJ
collection	DOAJ
language	EN
topic	Medicine R Science Q
spellingShingle	Medicine R Science Q Zhiwei Ma Juntao Li Chunyu Liu Chenglin Sun Mi Zhou High Pressure Spectroscopic Investigation on Proton Transfer in Squaric Acid and 4,4′-Bipyridine Co-crystal
description	Abstract In attempt to the obtain detailed geometric information of proton transfer compound (subsequently denote as SQBP) formed between squaric acid (SQ)and 4,4′-bipyridine(BP), and to investigate the mechanisms of pressure-induced double proton transfer and related structural phase transition, we carried out in-situ high pressure Raman spectroscopy of SQBP up to 20 GPa. A solid-solid phase transition together with double proton transfer phenomenon was confirmed by Raman spectroscopy at about 1.5 GPa, and the activation of C = O stretching mode in Raman spectra indicates a square-ring structure of SQ with four symmetric C = O bond formation. These results are further supported by first-principals calculations and in-situ high pressure infrared absorption spectroscopy. Additionally, Raman intensity analysis suggests that a higher-order phase transition with planar BP molecular structure occurred in the pressure range of 3~6 GPa. As a result, the π electron delocalization effect in BP dominated the intensity enhancement of C = O stretching mode in SQ. To the best of our knowledge, this is the first time observation of the intensity enhancement of proton donor’s normal modes induced by proton acceptor’s π electron delocalization.
format	article
author	Zhiwei Ma Juntao Li Chunyu Liu Chenglin Sun Mi Zhou
author_facet	Zhiwei Ma Juntao Li Chunyu Liu Chenglin Sun Mi Zhou
author_sort	Zhiwei Ma
title	High Pressure Spectroscopic Investigation on Proton Transfer in Squaric Acid and 4,4′-Bipyridine Co-crystal
title_short	High Pressure Spectroscopic Investigation on Proton Transfer in Squaric Acid and 4,4′-Bipyridine Co-crystal
title_full	High Pressure Spectroscopic Investigation on Proton Transfer in Squaric Acid and 4,4′-Bipyridine Co-crystal
title_fullStr	High Pressure Spectroscopic Investigation on Proton Transfer in Squaric Acid and 4,4′-Bipyridine Co-crystal
title_full_unstemmed	High Pressure Spectroscopic Investigation on Proton Transfer in Squaric Acid and 4,4′-Bipyridine Co-crystal
title_sort	high pressure spectroscopic investigation on proton transfer in squaric acid and 4,4′-bipyridine co-crystal
publisher	Nature Portfolio
publishDate	2017
url	https://doaj.org/article/1ba6618b27b042788053850c96948bb9
work_keys_str_mv	AT zhiweima highpressurespectroscopicinvestigationonprotontransferinsquaricacidand44bipyridinecocrystal AT juntaoli highpressurespectroscopicinvestigationonprotontransferinsquaricacidand44bipyridinecocrystal AT chunyuliu highpressurespectroscopicinvestigationonprotontransferinsquaricacidand44bipyridinecocrystal AT chenglinsun highpressurespectroscopicinvestigationonprotontransferinsquaricacidand44bipyridinecocrystal AT mizhou highpressurespectroscopicinvestigationonprotontransferinsquaricacidand44bipyridinecocrystal
_version_	1718394382742192128

High Pressure Spectroscopic Investigation on Proton Transfer in Squaric Acid and 4,4′-Bipyridine Co-crystal

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