Reduction-Triggered Self-Assembly of Nanoscale Molybdenum Oxide Molecular Clusters
Abstract
The understanding of the formation mechanism of giant molecular clusters is an essential requirement for rational design and synthesis of cluster-based nano-materials with required morphologies and functionalities. Here, typical synthetic reactions of a 2.9 nm spherical molybdenum oxide cluster, {Mo132} (Formula: [MoVI72MoV60O372(CH3COO)30(H2O)72]42-) with systematically varied reaction parameters have been fully explored for the morphologies and concentration of products, reduction of metal centers, and chemical environments of organic ligands. The growth of these clusters shows a typical sigmoid curve, suggesting a general multi-step self-assembly mechanism for the formation of giant molecular clusters. The reaction starts with a lag phase period when partial MoVI centers of molybdate precursors are reduced to form {MoV2(acetate)} structures under the coordination effect of the acetate groups. Once the concentration of {MoV2(acetate)} reaches a critical value, it triggers the co-assembly of MoV and MoVI species into the giant clusters.
- Authors:
-
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Inst. Max Von Laue Paul Langevin, Grenoble (France)
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Center for Nanophase Materials Sciences (CNMS); Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States). Spallation Neutron Source (SNS); Argonne National Laboratory (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1324096
- Alternate Identifier(s):
- OSTI ID: 1368099
- Grant/Contract Number:
- AC05-00OR22725; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of the American Chemical Society
- Additional Journal Information:
- Journal Volume: 138; Journal Issue: 33; Journal ID: ISSN 0002-7863
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Yin, Panchao, Wu, Bin, Li, Tao, Bonnesen, Peter V., Hong, Kunlun, Seifert, Soenke, Porcar, Lionel, Do, Changwoo, and Keum, Jong Kahk. Reduction-Triggered Self-Assembly of Nanoscale Molybdenum Oxide Molecular Clusters. United States: N. p., 2016.
Web. doi:10.1021/jacs.6b05882.
Yin, Panchao, Wu, Bin, Li, Tao, Bonnesen, Peter V., Hong, Kunlun, Seifert, Soenke, Porcar, Lionel, Do, Changwoo, & Keum, Jong Kahk. Reduction-Triggered Self-Assembly of Nanoscale Molybdenum Oxide Molecular Clusters. United States. https://doi.org/10.1021/jacs.6b05882
Yin, Panchao, Wu, Bin, Li, Tao, Bonnesen, Peter V., Hong, Kunlun, Seifert, Soenke, Porcar, Lionel, Do, Changwoo, and Keum, Jong Kahk. Tue .
"Reduction-Triggered Self-Assembly of Nanoscale Molybdenum Oxide Molecular Clusters". United States. https://doi.org/10.1021/jacs.6b05882. https://www.osti.gov/servlets/purl/1324096.
@article{osti_1324096,
title = {Reduction-Triggered Self-Assembly of Nanoscale Molybdenum Oxide Molecular Clusters},
author = {Yin, Panchao and Wu, Bin and Li, Tao and Bonnesen, Peter V. and Hong, Kunlun and Seifert, Soenke and Porcar, Lionel and Do, Changwoo and Keum, Jong Kahk},
abstractNote = {The understanding of the formation mechanism of giant molecular clusters is an essential requirement for rational design and synthesis of cluster-based nano-materials with required morphologies and functionalities. Here, typical synthetic reactions of a 2.9 nm spherical molybdenum oxide cluster, {Mo132} (Formula: [MoVI72MoV60O372(CH3COO)30(H2O)72]42-) with systematically varied reaction parameters have been fully explored for the morphologies and concentration of products, reduction of metal centers, and chemical environments of organic ligands. The growth of these clusters shows a typical sigmoid curve, suggesting a general multi-step self-assembly mechanism for the formation of giant molecular clusters. The reaction starts with a lag phase period when partial MoVI centers of molybdate precursors are reduced to form {MoV2(acetate)} structures under the coordination effect of the acetate groups. Once the concentration of {MoV2(acetate)} reaches a critical value, it triggers the co-assembly of MoV and MoVI species into the giant clusters.},
doi = {10.1021/jacs.6b05882},
journal = {Journal of the American Chemical Society},
number = 33,
volume = 138,
place = {United States},
year = {Tue Jul 26 00:00:00 EDT 2016},
month = {Tue Jul 26 00:00:00 EDT 2016}
}
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Works referenced in this record:
From serendipity to design of polyoxometalates at the nanoscale, aesthetic beauty and applications
journal, January 2012
- Cronin, Leroy; Müller, Achim
- Chemical Society Reviews, Vol. 41, Issue 22
Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles
journal, November 2011
- Chakrabarty, Rajesh; Mukherjee, Partha Sarathi; Stang, Peter J.
- Chemical Reviews, Vol. 111, Issue 11, p. 6810-6918
Molecular containers
journal, January 2015
- Ballester, Pablo; Fujita, Makoto; Rebek, Julius
- Chemical Society Reviews, Vol. 44, Issue 2
Modular and predictable assembly of porous organic molecular crystals
journal, June 2011
- Jones, James T. A.; Hasell, Tom; Wu, Xiaofeng
- Nature, Vol. 474, Issue 7351
Polyoxometalate clusters, nanostructures and materials: From self assembly to designer materials and devices
journal, January 2007
- Long, De-Liang; Burkholder, Eric; Cronin, Leroy
- Chem. Soc. Rev., Vol. 36, Issue 1
Introduction: PolyoxometalatesMulticomponent Molecular Vehicles To Probe Fundamental Issues and Practical Problems
journal, February 1998
- Hill, C. L.
- Chemical Reviews, Vol. 98, Issue 1
Reversible electron-transfer reactions within a nanoscale metal oxide cage mediated by metallic substrates
journal, March 2008
- Fleming, Christopher; Long, De-Liang; McMillan, Nicola
- Nature Nanotechnology, Vol. 3, Issue 4
Design and fabrication of memory devices based on nanoscale polyoxometalate clusters
journal, November 2014
- Busche, Christoph; Vilà-Nadal, Laia; Yan, Jun
- Nature, Vol. 515, Issue 7528
Quantum oscillations in a molecular magnet
journal, May 2008
- Bertaina, S.; Gambarelli, S.; Mitra, T.
- Nature, Vol. 453, Issue 7192
From linking of metal-oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry
journal, January 2012
- Müller, Achim; Gouzerh, Pierre
- Chemical Society Reviews, Vol. 41, Issue 22
Polyoxometalates: Very Large ClustersNanoscale Magnets
journal, February 1998
- Müller, Achim; Peters, Frank; Pope, Michael T.
- Chemical Reviews, Vol. 98, Issue 1
Unveiling the Transient Template in the Self-Assembly of a Molecular Oxide Nanowheel
journal, December 2009
- Miras, H. N.; Cooper, G. J. T.; Long, D. -L.
- Science, Vol. 327, Issue 5961
Time-Resolved Self-Assembly of a Fullerene-Topology Core–Shell Cluster Containing 68 Uranyl Polyhedra
journal, January 2012
- Qiu, Jie; Ling, Jie; Sui, Audrey
- Journal of the American Chemical Society, Vol. 134, Issue 3
X-ray and Neutron Scattering Study of the Formation of Core–Shell-Type Polyoxometalates
journal, February 2016
- Yin, Panchao; Wu, Bin; Mamontov, Eugene
- Journal of the American Chemical Society, Vol. 138, Issue 8
On the Origin of the Cation Templated Self-Assembly of Uranyl-Peroxide Nanoclusters
journal, December 2010
- Miró, Pere; Pierrefixe, Simon; Gicquel, Mickaël
- Journal of the American Chemical Society, Vol. 132, Issue 50
X-Ray crystallographic determination of the structure of the isopolyanion [Mo 36 O 112 (H 2 O) 16 ] 8– in the compound K 8 [Mo 36 O 112 (H 2 O) 16 ]·36H 2 O
journal, January 1979
- Paulat-Böschen, Irene
- J. Chem. Soc., Chem. Commun., Issue 17
Self-assembly of a novel nanoscale giant cluster: [Mo176O496(OH)32(H2O)80]†
journal, January 1998
- Jiang, Chang-Chun; Wei, Yong-Ge; Liu, Qun
- Chemical Communications, Issue 18
Photochemical Formation of Tire-Shaped Molybdenum Blues: Topology of a Defect Anion, [Mo142O432H28(H2O)58]12−
journal, January 2002
- Yamase, Toshihiro; Prokop, Petra V.
- Angewandte Chemie International Edition, Vol. 41, Issue 3
Investigating the Formation of “Molybdenum Blues” with Gel Electrophoresis and Mass Spectrometry
journal, May 2015
- Nakamura, Ippei; Miras, Haralampos N.; Fujiwara, Aya
- Journal of the American Chemical Society, Vol. 137, Issue 20
Organizational Forms of Matter: An Inorganic Super Fullerene and Keplerate Based on Molybdenum Oxide
journal, December 1998
- Müller, Achim; Krickemeyer, Erich; Bögge, Hartmut
- Angewandte Chemie International Edition, Vol. 37, Issue 24
Capsules with Highly Active Pores and Interiors: Versatile Platforms at the Nanoscale
journal, March 2014
- Müller, Achim; Gouzerh, Pierre
- Chemistry - A European Journal, Vol. 20, Issue 17
Molecular growth from a Mo176 to a Mo248 cluster
journal, January 1999
- Müller, A.; Shah, Syed Q. N.; Bögge, H.
- Nature, Vol. 397, Issue 6714
A multiplatform code for the analysis of energy-dispersive X-ray fluorescence spectra
journal, January 2007
- Solé, V. A.; Papillon, E.; Cotte, M.
- Spectrochimica Acta Part B: Atomic Spectroscopy, Vol. 62, Issue 1
Small Angle Neutron Scattering Studies of the Structure and Interaction in Micellar and Microemulsion Systems
journal, October 1986
- Chen, S. H.
- Annual Review of Physical Chemistry, Vol. 37, Issue 1
Water Repellency in Hydrophobic Nanocapsules-Molecular View on Dewetting
journal, April 2014
- Müller, Achim; Garai, Somenath; Schäffer, Christian
- Chemistry - A European Journal, Vol. 20, Issue 22
Studies on the Structure of Cationic Dimer of Molybdenum(VI) in Acidic Solution by XANES and EXAFS
journal, July 1987
- Yokoi, Kunihiko; Matsubayashi, Nobuyuki; Miyanaga, Takafumi
- Chemistry Letters, Vol. 16, Issue 7
Studies on the structure of molybdenum(VI) in acidic solution by xanes and exafs
journal, April 1993
- Yokoi, Kunihiko; Matsubayashi, Nobuyuki; Miyanaga, Takafumi
- Polyhedron, Vol. 12, Issue 8
X-ray absorption edge and EXAFS spectroscopic studies of molybdenum ions in aqueous solution
journal, February 1983
- Cramer, Stephen P.; Eidem, P. K.; Paffett, M. T.
- Journal of the American Chemical Society, Vol. 105, Issue 4
The molybdenum site of nitrogenase. Preliminary structural evidence from x-ray absorption spectroscopy
journal, May 1978
- Cramer, Stephen P.; Hodgson, Keith O.; Gillum, William O.
- Journal of the American Chemical Society, Vol. 100, Issue 11
Flexible Pores of a Metal Oxide-Based Capsule Permit Entry of Comparatively Larger Organic Guests
journal, May 2009
- Ziv, Ayala; Grego, Alina; Kopilevich, Sivil
- Journal of the American Chemical Society, Vol. 131, Issue 18
Spontaneous self-assembly of a giant spherical metal-oxide Keplerate: addition of one building block induces “immediate” formation of the complementary one from a constitutional dynamic library
journal, January 2012
- Schäffer, Christian; Todea, Ana Maria; Gouzerh, Pierre
- Chem. Commun., Vol. 48, Issue 3
Mapping the formation areas of giant molybdenum blue clusters: a spectroscopic study
journal, January 2012
- Botar, Bogdan; Ellern, Arkady; Kögerler, Paul
- Dalton Transactions, Vol. 41, Issue 29
En route from the mystery of molybdenum blue via related manipulatable building blocks to aspects of materials science
journal, October 2003
- Müller, A.; Roy, S.
- Coordination Chemistry Reviews, Vol. 245, Issue 1-2
From simple building blocks to structures with increasing size and complexity
journal, February 1999
- Müller, A.; Kögerler, P.
- Coordination Chemistry Reviews, Vol. 182, Issue 1
A Spherical 24 Butyrate Aggregate with a Hydrophobic Cavity in a Capsule with Flexible Pores: Confinement Effects and Uptake-Release Equilibria at Elevated Temperatures
journal, October 2009
- Schäffer, Christian; Bögge, Hartmut; Merca, Alice
- Angewandte Chemie International Edition, Vol. 48, Issue 43
Hydrophobic Interactions and Clustering in a Porous Capsule: Option to Remove Hydrophobic Materials from Water
journal, July 2011
- Schäffer, Christian; Todea, Ana Maria; Bögge, Hartmut
- Chemistry - A European Journal, Vol. 17, Issue 35
Cation Templating and Electronic Structure Effects in Uranyl Cage Clusters Probed by the Isolation of Peroxide-Bridged Uranyl Dimers
journal, April 2015
- Qiu, Jie; Vlaisavljevich, Bess; Jouffret, Laurent
- Inorganic Chemistry, Vol. 54, Issue 9
Works referencing / citing this record:
The applications of small-angle X-ray scattering in studying nano-scaled polyoxometalate clusters in solutions
journal, April 2018
- Li, Mu; Zhang, Mingxin; Wang, Weiyu
- Journal of Nanoparticle Research, Vol. 20, Issue 5
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journal, February 2019
- Li, Mu; Yin, Panchao
- Journal of Applied Crystallography, Vol. 52, Issue 1
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journal, June 2018
- Wu, Yan-Lan; Li, Xin-Xiong; Qi, Yan-Jie
- Angewandte Chemie, Vol. 130, Issue 28
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journal, July 2019
- She, Shan; Li, Mu; Li, Qi
- ChemPlusChem, Vol. 84, Issue 11
Poly(ethylene glycol) nanocomposites of sub-nanometer metal oxide clusters for dynamic semi-solid proton conductive electrolytes
journal, January 2019
- Zheng, Zhao; Zhou, Qianjie; Li, Mu
- Chemical Science, Vol. 10, Issue 31
{Nb 288 O 768 (OH) 48 (CO 3 ) 12 }: A Macromolecular Polyoxometalate with Close to 300 Niobium Atoms
journal, June 2018
- Wu, Yan-Lan; Li, Xin-Xiong; Qi, Yan-Jie
- Angewandte Chemie International Edition, Vol. 57, Issue 28
Improved peroxidase-mimic property: Sustainable, high-efficiency interfacial catalysis with H2O2 on the surface of vesicles of hexavanadate-organic hybrid surfactants
journal, February 2018
- Chen, Kun; Bayaguud, Aruuhan; Li, Hui
- Nano Research, Vol. 11, Issue 3
Synthesis of polyoxometalate clusters using carbohydrates as reducing agents leads to isomer-selection
journal, January 2019
- Janusson, Eric; de Kler, Noël; Vilà-Nadal, Laia
- Chemical Communications, Vol. 55, Issue 41
Scattering functions of carved-ellipsoid-shaped particles
text, January 2019
- Li, Mu; Yin, Panchao
- International Union of Crystallography (IUCr)
Poly(ethylene glycol) nanocomposites of sub-nanometer metal oxide clusters for dynamic semi-solid proton conductive electrolytes
journal, January 2019
- Zheng, Zhao; Zhou, Qianjie; Li, Mu
- Chemical Science, Vol. 10, Issue 31