Versatile Interplay of Chalcogenide and Dichalcogenide Anions in the Thiovanadate Ba₇S(VS₃O)₂(S₂)₃ and Its Selenide Derivatives: Elaboration and DFT Meta-GGA Study.

Almoussawi, Batoul ORCID: 0000-0001-6626-4453, Kageyama, Hiroshi ORCID: 0000-0002-3911-9864, Roussel, Pascal ORCID: 0000-0001-7243-7293 and Kabbour, Houria ORCID: 0000-0002-9081-3261 (2023) Versatile Interplay of Chalcogenide and Dichalcogenide Anions in the Thiovanadate Ba₇S(VS₃O)₂(S₂)₃ and Its Selenide Derivatives: Elaboration and DFT Meta-GGA Study. ACS organic & inorganic Au, 3 (3). pp. 158-170.

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Abstract

Oxychalcogenides are emerging as promising alternative candidates for a variety of applications including for energy. Only few phases among them show the presence of Q-Q bonds (Q = chalcogenide anion) while they drastically alter the electronic structure and allow further structural flexibility. Four original oxy(poly)chalcogenide compounds in the system Ba-V-Q-O (Q = S, Se) were synthesized, characterized, and studied using density functional theory (DFT). The new structure type found for Ba₇V₂O₂S₁₃, which can be written as Ba₇S(VS₃O)₂(S₂)₃, was substituted to yield three selenide derivatives Ba₇V₂O₂S_9.304Se_3.696, Ba₇V₂O₂S_7.15Se_5.85, and Ba₇V₂O₂S_6.85Se_6.15. They represent original multiple-anion lattices and first members in the system Ba-V-Se-S-O. They exhibit in the first layer heteroleptic tetrahedra V⁵⁺S₃O and isolated Q^2- anions and in the second layer dichalcogenide pairs (Q₂)^2- with Q = S or Se. Selenide derivatives were attempted by targeting the selective substitution of isolated Q^2- or (Q₂)^2- (in distinct layers) or both by selenide, but it systematically led to concomitant and partial substitution of both sites. A DFT meta-GGA study showed that selective substitution yields local constraints due to rigid VO₃S and pairs. Experimentally, incorporation of selenide in both layers avoids geometrical mismatch and constraints. In such systems, we show that the interplay between the O/S anionic ratio around V⁵⁺, together with the presence/nature of the dichalcogenides (Q₂)^2- and isolated Q^2-, impacts in unique manners the band gap and provides a rich background to tune the band gap and the symmetry.

Item Type:	Article
Divisions:	Faculty of Science and Engineering > School of Physical Sciences
Depositing User:	Symplectic Admin
Date Deposited:	29 Nov 2023 16:12
Last Modified:	29 Nov 2023 16:12
DOI:	10.1021/acsorginorgau.3c00006
Open Access URL:	https://doi.org/10.1021/acsorginorgau.3c00006
Related URLs:	Author Publisher
URI:	https://livrepository.liverpool.ac.uk/id/eprint/3177064