TY - JOUR
T1 - Self-Assembly and Ionic-Lattice-like Secondary Structure of a Flexible Linear Polymer of Highly Charged Inorganic Building Blocks
AU - Zhang, Guanyun
AU - Gadot, Eyal
AU - Gan-Or, Gal
AU - Baranov, Mark
AU - Tubul, Tal
AU - Neyman, Alevtina
AU - Li, Mu
AU - Clotet, Anna
AU - Poblet, Josep M.
AU - Yin, Panchao
AU - Weinstock, Ira A.
N1 - Publisher Copyright:
Copyright © 2020 American Chemical Society.
PY - 2020/4/22
Y1 - 2020/4/22
N2 - Among molecular building blocks, metal oxide cluster anions and their countercations provide multiple options for the self-assembly of functional materials. Currently, however, rational design concepts are limited to electrostatic interactions with metal or organic countercations or to the attachment and subsequent reactions of functionalized organic ligands. We now demonstrate that bridging μ-oxo linkages can be used to string together a bifunctional Keggin anion building block, [PNb2Mo10O40]5- (1), the diniobium(V) analogue of [PV2Mo10O40]5- (2). Induction of μ-oxo ligation between the NbVO moieties of 1 in acetonitrile via step-growth polymerization gives linear polymers with entirely inorganic backbones, some comprising over 140 000 repeating units, each with a 3-charge, exceeding that of previously reported organic or inorganic polyelectrolytes. As the chain grows, its flexible μ-oxo-linked backbone, with associated countercations, coils into a compact 270 nm diameter spherical secondary structure as a result of electrostatic interactions not unlike those within ionic lattices. More generally, the findings point to new options for the rational design of multidimensional structures based on μ-oxo linkages between NbVO-functionalized building blocks.
AB - Among molecular building blocks, metal oxide cluster anions and their countercations provide multiple options for the self-assembly of functional materials. Currently, however, rational design concepts are limited to electrostatic interactions with metal or organic countercations or to the attachment and subsequent reactions of functionalized organic ligands. We now demonstrate that bridging μ-oxo linkages can be used to string together a bifunctional Keggin anion building block, [PNb2Mo10O40]5- (1), the diniobium(V) analogue of [PV2Mo10O40]5- (2). Induction of μ-oxo ligation between the NbVO moieties of 1 in acetonitrile via step-growth polymerization gives linear polymers with entirely inorganic backbones, some comprising over 140 000 repeating units, each with a 3-charge, exceeding that of previously reported organic or inorganic polyelectrolytes. As the chain grows, its flexible μ-oxo-linked backbone, with associated countercations, coils into a compact 270 nm diameter spherical secondary structure as a result of electrostatic interactions not unlike those within ionic lattices. More generally, the findings point to new options for the rational design of multidimensional structures based on μ-oxo linkages between NbVO-functionalized building blocks.
UR - http://www.scopus.com/inward/record.url?scp=85088859892&partnerID=8YFLogxK
U2 - 10.1021/jacs.0c01486
DO - 10.1021/jacs.0c01486
M3 - Article
C2 - 32233364
AN - SCOPUS:85088859892
SN - 0002-7863
VL - 142
SP - 7295
EP - 7300
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
IS - 16
ER -