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Title: Reduction-Triggered Self-Assembly of Nanoscale Molybdenum Oxide Molecular Clusters

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.6b05882· OSTI ID:1324096
 [1];  [2];  [3];  [1];  [1];  [3];  [4];  [1];  [1]
  1. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States)
  2. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States); Univ. of Tennessee, Knoxville, TN (United States)
  3. Argonne National Lab. (ANL), Argonne, IL (United States)
  4. Inst. Max Von Laue Paul Langevin, Grenoble (France)
+ Show Author Affiliations

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.

Research Organization:
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 Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC05-00OR22725; AC02-06CH11357
OSTI ID:
1324096
Alternate ID(s):
OSTI ID: 1368099
Journal Information:
Journal of the American Chemical Society, Vol. 138, Issue 33; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 27 works
Citation information provided by
Web of Science

References (37)

From serendipity to design of polyoxometalates at the nanoscale, aesthetic beauty and applications journal January 2012
Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles journal November 2011
Molecular containers journal January 2015
Modular and predictable assembly of porous organic molecular crystals journal June 2011
Polyoxometalate clusters, nanostructures and materials: From self assembly to designer materials and devices journal January 2007
Introduction:  PolyoxometalatesMulticomponent Molecular Vehicles To Probe Fundamental Issues and Practical Problems journal February 1998
Reversible electron-transfer reactions within a nanoscale metal oxide cage mediated by metallic substrates journal March 2008
Design and fabrication of memory devices based on nanoscale polyoxometalate clusters journal November 2014
Quantum oscillations in a molecular magnet journal May 2008
From linking of metal-oxide building blocks in a dynamic library to giant clusters with unique properties and towards adaptive chemistry journal January 2012
Polyoxometalates:  Very Large ClustersNanoscale Magnets journal February 1998
Unveiling the Transient Template in the Self-Assembly of a Molecular Oxide Nanowheel journal December 2009
Time-Resolved Self-Assembly of a Fullerene-Topology Core–Shell Cluster Containing 68 Uranyl Polyhedra journal January 2012
X-ray and Neutron Scattering Study of the Formation of Core–Shell-Type Polyoxometalates journal February 2016
On the Origin of the Cation Templated Self-Assembly of Uranyl-Peroxide Nanoclusters journal December 2010
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
Self-assembly of a novel nanoscale giant cluster: [Mo176O496(OH)32(H2O)80]† journal January 1998
Photochemical Formation of Tire-Shaped Molybdenum Blues: Topology of a Defect Anion, [Mo142O432H28(H2O)58]12− journal January 2002
Investigating the Formation of “Molybdenum Blues” with Gel Electrophoresis and Mass Spectrometry journal May 2015
Organizational Forms of Matter: An Inorganic Super Fullerene and Keplerate Based on Molybdenum Oxide journal December 1998
Capsules with Highly Active Pores and Interiors: Versatile Platforms at the Nanoscale journal March 2014
Molecular growth from a Mo176 to a Mo248 cluster journal January 1999
A multiplatform code for the analysis of energy-dispersive X-ray fluorescence spectra journal January 2007
Small Angle Neutron Scattering Studies of the Structure and Interaction in Micellar and Microemulsion Systems journal October 1986
Water Repellency in Hydrophobic Nanocapsules-Molecular View on Dewetting journal April 2014
Studies on the Structure of Cationic Dimer of Molybdenum(VI) in Acidic Solution by XANES and EXAFS journal July 1987
Studies on the structure of molybdenum(VI) in acidic solution by xanes and exafs journal April 1993
X-ray absorption edge and EXAFS spectroscopic studies of molybdenum ions in aqueous solution journal February 1983
The molybdenum site of nitrogenase. Preliminary structural evidence from x-ray absorption spectroscopy journal May 1978
Flexible Pores of a Metal Oxide-Based Capsule Permit Entry of Comparatively Larger Organic Guests journal May 2009
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
Mapping the formation areas of giant molybdenum blue clusters: a spectroscopic study journal January 2012
En route from the mystery of molybdenum blue via related manipulatable building blocks to aspects of materials science journal October 2003
From simple building blocks to structures with increasing size and complexity journal February 1999
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
Hydrophobic Interactions and Clustering in a Porous Capsule: Option to Remove Hydrophobic Materials from Water journal July 2011
Cation Templating and Electronic Structure Effects in Uranyl Cage Clusters Probed by the Isolation of Peroxide-Bridged Uranyl Dimers journal April 2015

Cited By (9)

The applications of small-angle X-ray scattering in studying nano-scaled polyoxometalate clusters in solutions journal April 2018
Scattering functions of carved-ellipsoid-shaped particles journal February 2019
{Nb 288 O 768 (OH) 48 (CO 3 ) 12 }: A Macromolecular Polyoxometalate with Close to 300 Niobium Atoms journal June 2018
Unprecedented Halide‐Ion Binding and Catalytic Activity of Nanoscale Anionic Metal Oxide Clusters journal July 2019
Poly(ethylene glycol) nanocomposites of sub-nanometer metal oxide clusters for dynamic semi-solid proton conductive electrolytes journal January 2019
{Nb 288 O 768 (OH) 48 (CO 3 ) 12 }: A Macromolecular Polyoxometalate with Close to 300 Niobium Atoms journal June 2018
Improved peroxidase-mimic property: Sustainable, high-efficiency interfacial catalysis with H2O2 on the surface of vesicles of hexavanadate-organic hybrid surfactants journal February 2018
Synthesis of polyoxometalate clusters using carbohydrates as reducing agents leads to isomer-selection journal January 2019
Scattering functions of carved-ellipsoid-shaped particles text January 2019

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