Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
Polyoxometalates from gases: Mineral-inspired synthesis and characterization of novel compounds containing [M⊂Cu12O8(AsO4)8]q- polyoxocuprate clusters (M = Ti(IV), Bi(III)). / Корняков, Илья Викторович; Кривовичев, Сергей Владимирович; Шиловских, Владимир Владимирович; Калашникова, Софья Александровна; Бочаров, Владимир Николаевич.
в: Inorganic Chemistry Communications, Том 157, 111435, 01.11.2023.Результаты исследований: Научные публикации в периодических изданиях › статья › Рецензирование
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TY - JOUR
T1 - Polyoxometalates from gases: Mineral-inspired synthesis and characterization of novel compounds containing [M⊂Cu12O8(AsO4)8]q- polyoxocuprate clusters (M = Ti(IV), Bi(III))
AU - Корняков, Илья Викторович
AU - Кривовичев, Сергей Владимирович
AU - Шиловских, Владимир Владимирович
AU - Калашникова, Софья Александровна
AU - Бочаров, Владимир Николаевич
PY - 2023/11/1
Y1 - 2023/11/1
N2 - A novel type of polyoxocuprate (POCu) clusters, [M⊂Cu12O8(AsO4)8]q- (M = Ti(IV), Bi(III)), with a cubooctahedral arrangement of Cu2+ cations, have been prepared by chemical vapor transport reactions (CVT) using the methodology inspired by mineralogical discoveries at volcanic fumaroles of the Tolbachik volcano (Kamchatka peninsula, Russia). Three new compounds, Na21Cl6F[TiF6][TiCu12O8(AsO4)8] (1), Na18Cl6[TiCu12O8(AsO4)8] (2), and Na18Cl5[BiCu12O8(AsO4)8] (3), prepared under low-vacuum conditions, contain the {[M⊂Cu12O8](AsO4)8} (M = Ti4+, Fe3+) clusters with a Keggin-ion-like cubooctahedral arrangement of Cu2+ cations encapsulating Mn+ cations strikingly similar to the {[Pd13O8]L8]q- polyoxoanions observed in polyoxopalladates. The packing modes of clusters in different structures are different, with the structures of 1 and 3 based upon cubic-close-packing and hexagonal-close-packing arrangements, respectively. The packing of clusters in 2 is rather complex that results in its extreme structural complexity with the amount of Shannon structural information per unit cell exceeding 3000 bits. In the title compounds, the POCu clusters are embedded into salt matrices and therefore can be considered as an inverse analogue of salt-inclusion compounds, i.e., as inclusion-in-salt compounds. The successful synthesis of new types of POCu clusters using the CVT techniques opens up a new synthetic pathway for the exploration of polyoxocuprates with promising interesting structures and physical properties.
AB - A novel type of polyoxocuprate (POCu) clusters, [M⊂Cu12O8(AsO4)8]q- (M = Ti(IV), Bi(III)), with a cubooctahedral arrangement of Cu2+ cations, have been prepared by chemical vapor transport reactions (CVT) using the methodology inspired by mineralogical discoveries at volcanic fumaroles of the Tolbachik volcano (Kamchatka peninsula, Russia). Three new compounds, Na21Cl6F[TiF6][TiCu12O8(AsO4)8] (1), Na18Cl6[TiCu12O8(AsO4)8] (2), and Na18Cl5[BiCu12O8(AsO4)8] (3), prepared under low-vacuum conditions, contain the {[M⊂Cu12O8](AsO4)8} (M = Ti4+, Fe3+) clusters with a Keggin-ion-like cubooctahedral arrangement of Cu2+ cations encapsulating Mn+ cations strikingly similar to the {[Pd13O8]L8]q- polyoxoanions observed in polyoxopalladates. The packing modes of clusters in different structures are different, with the structures of 1 and 3 based upon cubic-close-packing and hexagonal-close-packing arrangements, respectively. The packing of clusters in 2 is rather complex that results in its extreme structural complexity with the amount of Shannon structural information per unit cell exceeding 3000 bits. In the title compounds, the POCu clusters are embedded into salt matrices and therefore can be considered as an inverse analogue of salt-inclusion compounds, i.e., as inclusion-in-salt compounds. The successful synthesis of new types of POCu clusters using the CVT techniques opens up a new synthetic pathway for the exploration of polyoxocuprates with promising interesting structures and physical properties.
KW - Chemical vapor transport reactions
KW - Mineral-inspired chemistry
KW - Polyoxocuprates
KW - Structural complexity
KW - Targeted synthesis
UR - https://www.mendeley.com/catalogue/40e833b8-d9aa-3d77-aceb-8f022b0e3da6/
U2 - 10.1016/j.inoche.2023.111435
DO - 10.1016/j.inoche.2023.111435
M3 - Article
VL - 157
JO - Inorganic Chemistry Communication
JF - Inorganic Chemistry Communication
SN - 1387-7003
M1 - 111435
ER -
ID: 114735921