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 -