TY - JOUR
T1 - Polyoxoniobates with the long-sought feature of face-sharing octahedra stabilized by Te(iv)
T2 - a synthetic analogue of natural minerals
AU - Zhen, Ni
AU - Li, Run Han
AU - Xue, Binghui
AU - Liu, Jingjing
AU - Xu, Shan
AU - Zhang, Chao
AU - Lei, Peng
AU - Dong, Jing
AU - Chi, Yingnan
AU - Yin, Panchao
AU - Lan, Ya Qian
AU - Hu, Changwen
N1 - Publisher Copyright:
This journal is © the Partner Organisations, 2026
PY - 2026/1/20
Y1 - 2026/1/20
N2 - Polyoxometalates (POMs) are primarily constructed from {MO6} octahedra connected through corner-, edge-, and/or face-sharing modes, with face-sharing being particularly rare. Silverton clusters, characterized by their face-sharing {MO6} octahedra, have been reported for Mo and W. However, Nb-based Silverton and polyoxoniobates (PONbs) with face-sharing octahedra have not yet been synthesized, despite their occurrence in natural minerals. Herein, [(Nb13O42){Te3(B-α-TeNb9O33)}4] (1a) and its trivacant structure [(Nb10O36){Te3(B-α-TeNb9O33)}4] (2a) with the long-sought feature of face-sharing {NbO6} octahedra have been synthesized for the first time. In 1a, the central {Nb13O42}, consisting of six sets of face-sharing {Nb2O9} and a central Nb, is surrounded by 12 Te(iv) ions anchored on four {TeNb9O33}. Notably, the observed {Nb13O42} can be viewed as both a synthetic analogue of natural minerals and a topological isomer of the classic Silverton cluster. Moreover, small angle X-ray scattering data analysis confirms the formation of the targeted PONb cluster and determines the co-existing key cluster species and their proportion during the assembly or disassembly process. Further computational studies indicate that highly charged Te(iv) ions play a key role in the stabilization of face-sharing PONbs. The photocatalytic hydrogen evolution activity of 1 has also been investigated. This work not only bridges the gap between natural and synthetic PONbs, but also deepens our understanding of the formation of face-sharing octahedra.
AB - Polyoxometalates (POMs) are primarily constructed from {MO6} octahedra connected through corner-, edge-, and/or face-sharing modes, with face-sharing being particularly rare. Silverton clusters, characterized by their face-sharing {MO6} octahedra, have been reported for Mo and W. However, Nb-based Silverton and polyoxoniobates (PONbs) with face-sharing octahedra have not yet been synthesized, despite their occurrence in natural minerals. Herein, [(Nb13O42){Te3(B-α-TeNb9O33)}4] (1a) and its trivacant structure [(Nb10O36){Te3(B-α-TeNb9O33)}4] (2a) with the long-sought feature of face-sharing {NbO6} octahedra have been synthesized for the first time. In 1a, the central {Nb13O42}, consisting of six sets of face-sharing {Nb2O9} and a central Nb, is surrounded by 12 Te(iv) ions anchored on four {TeNb9O33}. Notably, the observed {Nb13O42} can be viewed as both a synthetic analogue of natural minerals and a topological isomer of the classic Silverton cluster. Moreover, small angle X-ray scattering data analysis confirms the formation of the targeted PONb cluster and determines the co-existing key cluster species and their proportion during the assembly or disassembly process. Further computational studies indicate that highly charged Te(iv) ions play a key role in the stabilization of face-sharing PONbs. The photocatalytic hydrogen evolution activity of 1 has also been investigated. This work not only bridges the gap between natural and synthetic PONbs, but also deepens our understanding of the formation of face-sharing octahedra.
UR - https://www.scopus.com/pages/publications/105022305247
U2 - 10.1039/d5qi02031j
DO - 10.1039/d5qi02031j
M3 - Article
AN - SCOPUS:105022305247
SN - 2052-1545
VL - 13
SP - 456
EP - 464
JO - Inorganic Chemistry Frontiers
JF - Inorganic Chemistry Frontiers
IS - 2
ER -