Structural and Spectroscopic Properties of Benzoylpyridine-Based Hydrazones.

Autor: Mravec B; Institute of Chemistry, Faculty of Natural Sciences, Comenius University, Ilkovičova 6, 842 15, Bratislava, Slovakia., Marini A; Dipartimento di Fisica, Università di Genova, Via Dodecaneso 33, Genova, 16146, Italy., Tommasini M; Dipartimento di Chimica, Materiali e Ingegneria Chimica, Politecnico di Milano, P.zza Leonardo da Vinci 32, 20133, Milano, Italy., Filo J; Institute of Chemistry, Faculty of Natural Sciences, Comenius University, Ilkovičova 6, 842 15, Bratislava, Slovakia., Cigáň M; Institute of Chemistry, Faculty of Natural Sciences, Comenius University, Ilkovičova 6, 842 15, Bratislava, Slovakia., Mantero M; INAF - Osservatorio Astronomico di Brera, via Bianchi 46, 23807, Merate, Italy., Tosi S; Dipartimento di Fisica, Università di Genova, Via Dodecaneso 33, Genova, 16146, Italy.; INFN, Sezione di Genova, Via Dodecaneso 33, Genova, 16146, Italy., Canepa M; OPTMATLAB, Dipartimento di Fisica, Università di Genova, Via Dodecaneso 33, Genova, 16146, Italy., Bianco A; INAF - Osservatorio Astronomico di Brera, via Bianchi 46, 23807, Merate, Italy.
Jazyk: angličtina
Zdroj: Chemphyschem : a European journal of chemical physics and physical chemistry [Chemphyschem] 2021 Mar 17; Vol. 22 (6), pp. 533-541. Date of Electronic Publication: 2021 Feb 17.
DOI: 10.1002/cphc.202000941
Abstrakt: Photochromic hydrazones are attracting the attention in the field of photochromic systems especially due to their P-type character. To understand the structural features and their correlation with the spectroscopic data, UV-Vis, vibrational and ellipsometry spectroscopic techniques are employed with the support of density functional theory (DFT) calculations to three hydrazone derivatives based on benzoylpyridine. Interestingly, analysis of the structure shows the presence of two distinct rotamers around the pyridine ring with different energy and the well-defined conjugation path that changes due to E to Z isomerization especially in the hydrazone -C=N-NH part of the skeleton. IR and Raman spectra are analyzed, showing a higher selectivity in the Z form; moreover, the comparison with the normal modes proves the effect of the reaction on the backbone structure. The experimental results are in good agreement with the theoretical predictions, especially in the case of the Raman spectrum. The molecular polarization also changes from E to Z forms as predicted by DFT calculations. Spectroscopic ellipsometry on thin films of TOPAS doped with 10 %wt of the dimethylamino hydrazone derivative is used to prove such change at the molecular level. A modulation of the refractive index is observed, and it is correlated with the concentration of the active moiety and the calculated electronic polarizabilities.
(© 2021 Wiley-VCH GmbH.)
Databáze: MEDLINE
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