Octahedral {Ta6I12} Clusters

Maxim V. Shamshurin, Maxim A. Mikhaylov, Taisia Sukhikh, Enrico Benassi, Alexandra R. Tarkova, Alexey A. Prokhorikhin, Evgeniy I. Kretov, Michael A. Shestopalov, Pavel A. Abramov, Maxim N. Sokolov

Результат исследования: Научные публикации в периодических изданияхстатья

1 Цитирования (Scopus)


Ta powder reacts with I2 at 650 °C with the formation of Ta6I14, which belongs to the family of {M6(μ-X)12} clusters. It undergoes aquation with the formation of the intensely colored [Ta6I12(H2O)6]2+. The crystal structure was determined for [Ta6I12(H2O)6](BPh4)2·xH2O (Ta-Ta 2.9322(6) Å, Ta-I 2.8104(7) Å, Ta-O 2.3430(5) Å). With DMF, [Ta6I12(DMF)6]I2·xDMF was isolated (Ta-Ta 2.9500(2) Å, Ta-I 2.8310(4) Å, Ta-O 2.2880(7) Å). Cyclic voltammetry of [Ta6I12(H2O)6]2+ shows two consecutive quasi-reversible one-electron oxidations (E1/2 0.61 and 0.92 V vs Ag/AgCl). Reaction of Ta6I14 with Bu4NCN yields (Bu4N)4[Ta6I12(CN)6]·xCH3CN (Ta-Ta 2.9777(4) Å, Ta-I 2.8165(6) Å, Ta-C 2.2730(7) Å). Quantum chemical calculations reproduce well the experimental geometry of the aqua complex and show the essentially Ta-centered nature of both the HOMO and LUMO. The long-term stability of [Ta6I12(H2O)6]2+ solutions can be greatly enhanced in the presence of polystyrenesulfonate (PSS), which forms nanoparticle associates with the aqua complex in water (ca. 1 cluster per 3 PSS monomeric units).

Язык оригиналаанглийский
Страницы (с-по)9028-9035
Число страниц8
ЖурналInorganic Chemistry
Номер выпуска14
СостояниеОпубликовано - 24 июн 2019

Fingerprint Подробные сведения о темах исследования «Octahedral {Ta<sub>6</sub>I<sub>12</sub>} Clusters». Вместе они формируют уникальный семантический отпечаток (fingerprint).