Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Trapping an Unexpected/Unprecedented Hexanuclear Ce(III) Hydrolysis Product with Neutral 4‐Amino‐1,2,4‐triazole (in EN)

Journal Article · · European Journal of Inorganic Chemistry
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4]; ORCiD logo [5]; ORCiD logo [6]; ORCiD logo [2]; ORCiD logo [7]
  1. Univ. of Alabama, Tuscaloosa, AL (United States); Colorado School of Mines, Golden, CO (United States)
  2. Stockholm Univ. (Sweden); Aarhus Univ. (Denmark)
  3. Univ. of Alabama, Tuscaloosa, AL (United States)
  4. Linköping Univ., Norrköping (Sweden)
  5. Univ. of Alabama, Tuscaloosa, AL (United States); Univ. of Michigan, Ann Arbor, MI (United States)
  6. Uppsala Univ. (Sweden)
  7. Univ. of Alabama, Tuscaloosa, AL (United States); Stockholm Univ. (Sweden)
+ Show Author Affiliations

Using Ce(III) as both a representative lanthanide and actinide analog, the ability of mixtures of acidic and basic azoles to allow direct access to homoleptic N-donor f-element complexes in one pot reactions from hydrated salts as starting materials was examined by reacting mixtures of 4-amino-1,2,4-triazole (4-NH2-1,2,4-Triaz), 5-amino-tetrazole (5-NH2-HTetaz), and 1,2,3-triazole (1,2,3-HTriaz) in 1 : 1 and 1 : 3 ratios with CeCl3 ⋅ 7H2O, [C2mim]3[CeCl6] ([C2mim]+=1-ethyl-2-methylimidazolium), and Ce(NO3)3 ⋅ 6H2O. Although unsuccessful in our goal, structural analysis revealed that neutral 4-NH2-1,2,4-Triaz is structure directing via η2μ2κ2 bridging, with the formation of the dinuclear complexes [Ce2Cl2(μ2-4-NH2-1,2,4-Triaz)4(H2O)8]Cl4 ⋅ 4H2O, [Ce2(μ2-4-NH2-1,2,4-Triaz)4(4-NH2-1,2,4-Triaz)2(Cl)6], and [4-NH2-1,2,4-HTriaz][Ce2(μ2-4-NH2-1,2,4-Triaz)2(μ2-NO3)(NO3)6(H2O)2]. When the synthetic conditions favored hydrolysis, the hexanuclear Ce(III) complex [Ce6(μ3-O)4(μ3-OH)2(μ3-Cl)2(Cl)6(μ2-4-NH2-1,2,4-Triaz)12] ⋅ 7H2O was isolated. This unexpected hydrolysis product represents the first example of a high nuclearity lanthanide complex where all Ln atoms are pairwise connected through 12 N-donor ligands or 12 neutral bridging ligands of any type, a rare example of incorporation of non-oxo coordinating anions in the M6X8 core, and the first reported Ce(III) hexanuclear complex of this type.

Research Organization:
Univ. of Alabama, Tuscaloosa, AL (United States)
Sponsoring Organization:
National Science Foundation (NSF); Swedish Research Council (VR); USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
SC0019220
OSTI ID:
1999279
Journal Information:
European Journal of Inorganic Chemistry, Journal Name: European Journal of Inorganic Chemistry Journal Issue: 31 Vol. 26; ISSN 1099-0682; ISSN 1434-1948
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
EN

References (54)

Efficient and Long Lived Green Light‐Emitting Electrochemical Cells journal May 2020
The Structure of the Plutonium Oxide Nanocluster [Pu38O56Cl54(H2O)8]14− journal January 2008
Dinuclear Lanthanide Complexes Based on a Schiff-base Ligand: Free Lattice Solvent Inducing the Single Molecule Magnet Behavior of Dy2 Compound journal October 2018
Cerium(IV) Hexanuclear Clusters from Cerium(III) Precursors: Molecular Models for Oxidative Growth of Ceria Nanoparticles journal July 2015
Ready Access to Anhydrous Anionic Lanthanide Acetates by Using Imidazolium Acetate Ionic Liquids as the Reaction Medium journal August 2021
Structural Trends in Alkaline Earth and Rare Earth Metal 3,5‐Diisopropylpyrazolates journal January 2007
The Synthesis, Structures and Polymorphism of the Dimeric Trivalent Rare‐Earth 3,5‐Dimethylpyrazolate Complexes [Ln(Me 2 pz) 3 (thf)] 2 journal April 2014
First Evidence of a Water-Soluble Plutonium(IV) Hexanuclear Cluster: First Evidence of a Water-Soluble Plutonium(IV) Hexanuclear Cluster journal July 2016
Direct Synthesis of Spin‐Crossover Complexes: An Unexpectedly Revealed New Iron‐Triazolic Structure journal November 2020
Homo- and Heterovalent Polynuclear Cerium and Cerium/Manganese Aggregates journal November 2009
[Nd6(μ6‐O)(μ3‐OH)8(H2O)24]I8(H2O)12 ‐ the First Basic Rare Earth Iodide with an Oxygen‐centred M6X8‐Cluster Core journal February 2005
The Octanuclear Europium Cluster [bmpyr]6[Eu8(μ4‐O)(μ3‐OH)12(μ2‐OTf)14 (μ1‐Tf)2](HOTf)1.5 Obtained from the Ionic Liquid [bmpyr][OTf] journal August 2006
Energy-adjusted pseudopotentials for the rare earth elements journal January 1989
On the structures of dinuclear symmetric lanthanide complexes and the selectivity towards heterodinuclear complexes based on molecular modeling journal August 2019
Structural transformation from a coplanar layer to a linear chain by switchable coordination of exocyclic amino group journal December 2012
Structural diversity in Cu(II) and Cd(II) coordination complexes with 4-amino-1,2,4-triazole ligand journal May 2014
Three copper(II) 4-amino-1,2,4-triazole complexes containing differently deprotonated forms of 1,3,5-benzenetricarboxylic acid: Synthesis, structures and magnetism journal June 2012
Anhydrous vs Hydrated f-Element Acetate Polymers Dictated by the Stoichiometry of Protic Acidic/Basic Azole Mixtures journal March 2021
Accessing Lanthanide Tricyanomethanide Coordination Polymers Using Ionic Liquids journal March 2022
Forcing Dicyanamide Coordination to f-Elements by Dissolution in Dicyanamide-Based Ionic Liquids journal May 2020
Expansion of the Family of Molecular Nanoparticles of Cerium Dioxide and Their Catalytic Scavenging of Hydroxyl Radicals journal January 2021
Aqueous Speciation of Tetravalent Actinides in the Presence of Chloride and Nitrate Ligands journal September 2022
Nitrogen-Rich Copper(II) Bromate Complexes: an Exotic Class of Primary Explosives journal June 2018
Structures, Single-Molecule Magnets, and Fluorescent Properties of Four Dinuclear Lanthanide Complexes Based on 4-Azotriazolyl-3-hydroxy-2-naphthoic Acid journal April 2019
Multifunctionality in Two Families of Dinuclear Lanthanide(III) Complexes with a Tridentate Schiff-Base Ligand journal July 2019
Dehydration of UO 2 Cl 2 ·3H 2 O and Nd(NO 3 ) 3 ·6H 2 O with a Soft Donor Ligand and Comparison of Their Interactions through X-ray Diffraction and Theoretical Investigation journal February 2020
Solution and Solid-State Structural Chemistry of Actinide Hydrates and Their Hydrolysis and Condensation Products journal October 2012
XAFS and LIBD Investigation of the Formation and Structure of Colloidal Pu(IV) Hydrolysis Products journal July 2004
Cluster-Type Basic Lanthanide Iodides [M6(μ6-O)(μ3-OH)8(H2O)24]I8(H2O)8 (M = Nd, Eu, Tb, Dy) journal May 2006
Insights into the Origin of Cooperative Effects in the Spin Transition of [Fe(NH2trz)3](NO3)2: the Role of Supramolecular Interactions Evidenced in the Crystal Structure of [Cu(NH2trz)3](NO3)2·H2O journal May 2010
Use of Soft Heterocyclic N-Donor Ligands To Separate Actinides and Lanthanides journal June 2012
Plutonium(IV) Cluster with a Hexanuclear [Pu 6 (OH) 4 O 4 ] 12+ Core journal May 2013
Hydrolytic synthesis and structural characterization of five hexanuclear oxo-hydroxo lanthanideclusters journal January 2010
Pyrazolates advance cerium chemistry: a Ce III /Ce IV redox equilibrium with benzoquinone journal January 2017
Water molecule induced reversible single-crystal-to-single-crystal transformation between two trinuclear Fe( ii ) complexes with different spin crossover behaviour journal January 2018
Molecular nanoparticles of cerium dioxide: structure-directing effect of halide ions journal January 2020
Benchtop access to anhydrous actinide N-donor coordination complexes using ionic liquids journal January 2020
Dinuclear lanthanide complexes supported by a hybrid salicylaldiminato/calix[4]arene-ligand: synthesis, structure, and magnetic and luminescence properties of (HNEt3)[Ln2(HL)(L)] (Ln = SmIII, EuIII, GdIII, TbIII) journal January 2019
Two Ni/Co-substituted sandwich-type germanomolybdates based on an unprecedented trivacant polyanion [α-GeMo10O36]8− journal January 2020
Relevance of formation conditions to the size, morphology and local structure of intrinsic plutonium colloids journal January 2020
Counter anion dependent symmetry of CuII–4-amino-1,2,4-triazole polymeric chains journal January 2001
Flexible coordination environments of lanthanide complexes grown from chloride-based ionic liquids journal January 2008
The 1-D polymeric structure of the [Fe(NH2trz)3](NO3)2·nH2O (with n = 2) spin crossover compound proven by single crystal investigations journal January 2011
Self‐Consistent Molecular‐Orbital Methods. IX. An Extended Gaussian‐Type Basis for Molecular‐Orbital Studies of Organic Molecules journal January 1971
Self‐consistent molecular orbital methods 25. Supplementary functions for Gaussian basis sets journal April 1984
Density‐functional thermochemistry. III. The role of exact exchange journal April 1993
Development of the Colle-Salvetti correlation-energy formula into a functional of the electron density journal January 1988
Hexakis(μ2-4-amino-4H-1,2,4-triazole)hexachlorotricadmium(II) journal August 2005
An empirical correction for the influence of low-energy contamination journal November 2015
The Cambridge Structural Database
  • Groom, Colin R.; Bruno, Ian J.; Lightfoot, Matthew P.
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 72, Issue 2, p. 171-179 https://doi.org/10.1107/S2052520616003954
journal April 2016
Crystal structure refinement with SHELXL journal January 2015
SHELXT – Integrated space-group and crystal-structure determination journal January 2015
Separation of trivalent actinides and lanthanides using various ‘N’, ‘S’ and mixed ‘N,O’ donor ligands: a review journal September 2019
New insights in the formation processes of Pu(IV) colloids journal May 2009

Similar Records

Related Subjects

Chemistry
azoles
hydroxo clusters
lanthanides
oxo clusters
structure elucidation