Organoboron-Functionalization Enables the Hierarchical Assembly of Giant Polyoxometalate Nanocapsules

Shujun Li; Yanfang Zhou; Nana Ma; Jie Zhang; Zhiping Zheng; Carsten Streb; Xuenian Chen

doi:10.1002/anie.202003550

Organoboron-Functionalization Enables the Hierarchical Assembly of Giant Polyoxometalate Nanocapsules

Shujun Li
, Yanfang Zhou
, Nana Ma
, Jie Zhang
, Zhiping Zheng
, Carsten Streb
, Xuenian Chen

Chemistry & Biochemistry - Sci

Research output: Contribution to journal › Article › peer-review

58 Scopus citations

Abstract

The aggregation of molecular metal oxides into larger superstructures can bridge the gap between molecular compounds and solid-state materials. Here, we report that functionalization of polyoxotungstates with organo-boron substituents leads to giant polyoxometalate-based nanocapsules with dimensions of up to 4 nm. A “lock and key” mechanism enables the site-specific anchoring of aromatic organo-boronic acids to metal-functionalized Dawson anions [M₃P₂W₁₅O₆₂]⁹⁻ (M=Ta^V or Nb^V), resulting in unique nanocapsules containing up to twelve POM units. Experimental and theoretical studies provide initial insights into the role of the organo-boron moieties and the metal-functionalized POMs for the assembly of the giant aggregates. The study therefore lays the foundations for the design of organo-POM-based functional nanostructures.

Original language	English (US)
Pages (from-to)	8537-8540
Number of pages	4
Journal	Angewandte Chemie - International Edition
Volume	59
Issue number	22
DOIs	https://doi.org/10.1002/anie.202003550
State	Published - May 25 2020

Keywords

boronic acid
organo-functionalization
polyoxometalate
self-assembly
supramolecular chemistry

ASJC Scopus subject areas

Catalysis
General Chemistry

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10.1002/anie.202003550

Cite this

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title = "Organoboron-Functionalization Enables the Hierarchical Assembly of Giant Polyoxometalate Nanocapsules",

abstract = "The aggregation of molecular metal oxides into larger superstructures can bridge the gap between molecular compounds and solid-state materials. Here, we report that functionalization of polyoxotungstates with organo-boron substituents leads to giant polyoxometalate-based nanocapsules with dimensions of up to 4 nm. A “lock and key” mechanism enables the site-specific anchoring of aromatic organo-boronic acids to metal-functionalized Dawson anions [M3P2W15O62]9− (M=TaV or NbV), resulting in unique nanocapsules containing up to twelve POM units. Experimental and theoretical studies provide initial insights into the role of the organo-boron moieties and the metal-functionalized POMs for the assembly of the giant aggregates. The study therefore lays the foundations for the design of organo-POM-based functional nanostructures.",

keywords = "boronic acid, organo-functionalization, polyoxometalate, self-assembly, supramolecular chemistry",

author = "Shujun Li and Yanfang Zhou and Nana Ma and Jie Zhang and Zhiping Zheng and Carsten Streb and Xuenian Chen",

note = "Funding Information: This work was supported by the National Natural Science Foundation of China (grant nos. U1804253 and 21771057), the breeding programs of HTU (2019PL06) and the Shenzhen Nobel Prize Scientists Laboratory Project (C17213101). All calculations were supported by The High Performance Computing Center of Henan Normal University. C.S. gratefully acknowledges support by Ulm University, Helmholtz‐Institute Ulm and the Deutsche Forschungsgemeinschaft DFT (grant nos: STR1164/12, TRR234 “CataLight” (project no: 364549901)). Funding Information: This work was supported by the National Natural Science Foundation of China (grant nos. U1804253 and 21771057), the breeding programs of HTU (2019PL06) and the Shenzhen Nobel Prize Scientists Laboratory Project (C17213101). All calculations were supported by The High Performance Computing Center of Henan Normal University. C.S. gratefully acknowledges support by Ulm University, Helmholtz-Institute Ulm and the Deutsche Forschungsgemeinschaft DFT (grant nos: STR1164/12, TRR234 ?CataLight? (project no: 364549901)). Publisher Copyright: {\textcopyright} 2020 The Authors. Published by Wiley-VCH Verlag GmbH \& Co. KGaA.",

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AU - Zhou, Yanfang

AU - Ma, Nana

AU - Zhang, Jie

AU - Zheng, Zhiping

AU - Streb, Carsten

AU - Chen, Xuenian

N1 - Funding Information: This work was supported by the National Natural Science Foundation of China (grant nos. U1804253 and 21771057), the breeding programs of HTU (2019PL06) and the Shenzhen Nobel Prize Scientists Laboratory Project (C17213101). All calculations were supported by The High Performance Computing Center of Henan Normal University. C.S. gratefully acknowledges support by Ulm University, Helmholtz‐Institute Ulm and the Deutsche Forschungsgemeinschaft DFT (grant nos: STR1164/12, TRR234 “CataLight” (project no: 364549901)). Funding Information: This work was supported by the National Natural Science Foundation of China (grant nos. U1804253 and 21771057), the breeding programs of HTU (2019PL06) and the Shenzhen Nobel Prize Scientists Laboratory Project (C17213101). All calculations were supported by The High Performance Computing Center of Henan Normal University. C.S. gratefully acknowledges support by Ulm University, Helmholtz-Institute Ulm and the Deutsche Forschungsgemeinschaft DFT (grant nos: STR1164/12, TRR234 ?CataLight? (project no: 364549901)). Publisher Copyright: © 2020 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.

PY - 2020/5/25

Y1 - 2020/5/25

N2 - The aggregation of molecular metal oxides into larger superstructures can bridge the gap between molecular compounds and solid-state materials. Here, we report that functionalization of polyoxotungstates with organo-boron substituents leads to giant polyoxometalate-based nanocapsules with dimensions of up to 4 nm. A “lock and key” mechanism enables the site-specific anchoring of aromatic organo-boronic acids to metal-functionalized Dawson anions [M3P2W15O62]9− (M=TaV or NbV), resulting in unique nanocapsules containing up to twelve POM units. Experimental and theoretical studies provide initial insights into the role of the organo-boron moieties and the metal-functionalized POMs for the assembly of the giant aggregates. The study therefore lays the foundations for the design of organo-POM-based functional nanostructures.

AB - The aggregation of molecular metal oxides into larger superstructures can bridge the gap between molecular compounds and solid-state materials. Here, we report that functionalization of polyoxotungstates with organo-boron substituents leads to giant polyoxometalate-based nanocapsules with dimensions of up to 4 nm. A “lock and key” mechanism enables the site-specific anchoring of aromatic organo-boronic acids to metal-functionalized Dawson anions [M3P2W15O62]9− (M=TaV or NbV), resulting in unique nanocapsules containing up to twelve POM units. Experimental and theoretical studies provide initial insights into the role of the organo-boron moieties and the metal-functionalized POMs for the assembly of the giant aggregates. The study therefore lays the foundations for the design of organo-POM-based functional nanostructures.

KW - boronic acid

KW - organo-functionalization

KW - polyoxometalate

KW - self-assembly

KW - supramolecular chemistry

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AN - SCOPUS:85083498662

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JO - Angewandte Chemie - International Edition

JF - Angewandte Chemie - International Edition

IS - 22

ER -

Organoboron-Functionalization Enables the Hierarchical Assembly of Giant Polyoxometalate Nanocapsules

Abstract

Keywords

ASJC Scopus subject areas

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