Naslov
The reversible electron transfer within hydrochromic charge-transfer material containing pyridinium oxime and hexacyanoferrate(II) ions

Autori
Picek, Igor ; Foretić Blaženka ; Žilić, Dijana ; Šantić, Ana ; Popović, Jasminka

Vrsta, podvrsta i kategorija rada
Sažeci sa skupova, sažetak, znanstveni

Izvornik
27th Croatian Meeting of Chemists and Chemical Engineers: Book of Abstracts / Marković, Dean ; Meštrović, Ernest ; Namjesnik, Danijel ; Tomašić, Vesna - Zagreb : Hrvatsko kemijsko društvo, 2021, 174-174

Skup
27th Croatian Meeting of Chemists and Chemical Engineers

Mjesto i datum
Veli Lošinj, Hrvatska, 05.10.2021. - 08.10.2021

Vrsta sudjelovanja
Poster

Vrsta recenzije
Domaća recenzija

Ključne riječi
Hexacyanoferrate(II), pyridinium oximes, electron transfer

Sažetak
The complex of N-benzylpyridinium-4-oxime (BPA4+ ) and hexacyanoferrate(II) (HCF4–) has been recognized as the supramolecular charge-transfer material with distinct optical properties.[1] Herein, the novel insight into structural and electronic changes caused by dehydration of the reddish-brown (BPA4)4HCF·10H2O (1·10H2O) to blue (BPA4)4HCF (1) is presented. The crystal structure of 1 was solved by SCXRD and the temperature-induced dehydration was investigated by in-situ PXRD (Fig. 1). With increase in temperature, 1·10H2O subsequently releases water molecules yielding fully dehydrated complex 1 which swiftly transforms back to 1·10H2O with exposure to water (Fig. 1a), providing the evidence of a reversible hydrochromism. The crystal packing of 1, where the hydroxyl group within oxime moiety forms a direct H-bond with cyano ligand, differs significantly from 1·10H2O where the HCF4– core and BPA4+ are bridged via H- bonded water molecules (Fig. 1b). The in-situ ESR study at different temperatures supplemented with DC conductivity and DRS spectral changes revealed that such reversible structural reorganization leads to the one electron transfer from HCF4– to BPA4+ resulting in the formation of a stable radical BPA4• and a small quantity of BPA4•/HCF3– pair within complex 1.

Izvorni jezik
Engleski

Znanstvena područja
Kemija, Interdisciplinarne prirodne znanosti

POVEZANOST RADA