skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Thermodynamic Stability of Heterodimetallic [LnLn'] Complexes: Synthesis and DFT Studies

Journal Article · · Chemistry - A European Journal
 [1];  [2];  [3];  [3];  [3];  [4];  [5];  [6]; ORCiD logo [3]
  1. Barcelona Inst. of Science and Technology (BIST) (Spain). Inst. of Chemical Research of Catalonia (ICIQ)
  2. Barcelona Inst. of Science and Technology (BIST) (Spain). Inst. of Chemical Research of Catalonia (ICIQ); Univ. of Lisbon (Portugal). Faculty of Sciences, Center for Chemistry and Biochemistry (CQB), Center for Structural Chemistry (CQE) and Higher Technical inst.
  3. Univ. of Barcelona (Spain). Dept. of Inorganic Chemistry
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  5. Spanish National Research Council (CSIC) and the Univ. of Zaragoza (Spain). Aragon Materials Science Institute (ICMA)
  6. Barcelona Inst. of Science and Technology (BIST) (Spain). Inst. of Chemical Research of Catalonia (ICIQ); Rovira i Virgili Univ., Tarragona (Spain). Dept. of Physical and Inorganic Chemistry
+ Show Author Affiliations

The solid-state and solution configurations of the heterodimetallic complexes (Hpy)[LaEr(HL)3(NO3)(py)(H2O)] (1), (Hpy)[CeEr(HL)3(NO3)(py)(H2O)] (2), (Hpy)[CeGd(HL)3(NO3)(py)(H2O)] (3), (Hpy)[PrSm(HL)3(NO3)(py)(H2O)] (4), and (Hpy)2[LaYb(HL)3(NO3)(H2O)](NO3) (5), in which H3L is 6-(3-oxo-3-(2-hydroxyphenyl)propionyl)pyridine-2-carboxylic acid and py is pyridine, were analyzed experimentally and by using DFT calculations. Complexes 3, 4, and 5 are described here for the first time, and were analyzed by using single-crystal X-ray diffraction and mass spectrometry. The theoretical study was also extended to the [LaCe] and [LaLu] analogues. The results are consistent with a remarkable selectivity of the metal distribution within the molecule in the solid state, enhanced by the size difference between the different ions. This selectivity was reduced in solution, particularly for ions with the most similar radii. This unique entry into 4f–4f" heterometallic chemistry establishes for the first time the difference between the selectivity in solution and that in the solid state, as a result of changes to the coordination that follow the dissociation of terminal ligands upon dissolution of the complexes.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); European Research Council (ERC); Ministry of Economy and Enterprise (MINECO) (Spain); European Commission (EC); Foundation for Science and Technology (FCT) (Portugal)
Grant/Contract Number:
AC02-05CH11231; 258060 FuncMolQIP; CTQ2012‐32247; CTQ2015‐68370‐P; CTQ2014‐52824‐R; MAT2014‐53961‐R; 291787‐ICIQ‐IPMP; SFRH/BPD/110419/2015; SEV‐2013‐0319; 2014SGR409
OSTI ID:
1454490
Alternate ID(s):
OSTI ID: 1401274
Journal Information:
Chemistry - A European Journal, Vol. 23, Issue 21; Related Information: 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim; ISSN 0947-6539
Publisher:
ChemPubSoc EuropeCopyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 18 works
Citation information provided by
Web of Science

References (43)

Heterometallic 3d–4f single-molecule magnets journal January 2015
Synthesis and characterization of dinuclear heterometallic lanthanide complexes exhibiting MRI and luminescence response journal January 2010
Density-functional exchange-energy approximation with correct asymptotic behavior journal September 1988
Erratum: Density-functional approximation for the correlation energy of the inhomogeneous electron gas journal November 1986
Purely Heterometallic Lanthanide(III) Macrocycles through Controlled Assembly of Disulfide Bonds for Dual Color Emission journal February 2011
Managing the Computational Chemistry Big Data Problem: The ioChem-BD Platform journal December 2014
3d−4f Combined Chemistry: Synthetic Strategies and Magnetic Properties journal April 2009
Electron-Donating Alkoxy-Group-Driven Synthesis of Heteroleptic Tris(phthalocyaninato) Lanthanide(III) Triple-Deckers with Symmetrical Molecular Structure journal February 2005
Self-assembly between dicarboxylate ions and a binuclear europium complex: formation of stable adducts and heterometallic lanthanide complexes journal January 2011
Understanding, Controlling and Programming Cooperativity in Self-Assembled Polynuclear Complexes in Solution journal November 2009
Synthesis and Properties of a Family of Unsymmetric Dinuclear Complexes of Ln III (Ln = Eu, Gd, Tb) journal August 2010
Recent advances in dysprosium-based single molecule magnets: Structural overview and synthetic strategies journal June 2013
Synthesis and Spectroscopic Studies on Azo-Dye Derivatives of Polymetallic Lanthanide Complexes: Using Diazotization to Link Metal Complexes Together journal July 2009
Unequivocal Synthetic Pathway to Heterodinuclear (4f,4f′) Complexes: Magnetic Study of Relevant (LnIII, GdIII) and (GdIII, LnIII) Complexes journal August 2002
SHELXT – Integrated space-group and crystal-structure determination journal January 2015
Supramolecular Recognition of Heteropairs of Lanthanide Ions:  A Step toward Self-Assembled Bifunctional Probes journal January 2004
A multicenter numerical integration scheme for polyatomic molecules journal February 1988
Magnetic lanthanide–transition-metal organic–inorganic hybrid materials: From discrete clusters to extended frameworks journal December 2009
A Long Journey in Lanthanide Chemistry: From Fundamental Crystallogenesis Studies to Commercial Anticounterfeiting Taggants journal April 2016
Structure-Based Description of a Step-by-Step Synthesis of Homo- and Heterodinuclear (4f, 4f ‘) Lanthanide Complexes journal October 2003
A short history of SHELX journal December 2007
Tuneable Intramolecular Intermetallic Interactions as a New Tool for Programming Linear Heterometallic 4f−4f Complexes journal October 2007
Revised Ionic Radii of Lanthanoid(III) Ions in Aqueous Solution journal May 2011
Two Discrete Ln 12 Shelf-Shaped Clusters: Magnetic Studies Reveal a Significant Cryogenic Magnetocaloric Effect and Slow Magnetic Relaxation : Two Discrete Ln journal October 2016
Rare-Earth Metal Oxo/Hydroxo Clusters - Synthesis, Structures, and Applications journal January 2016
Ln 3 Q 9 as a Molecular Framework for Ion-Size-Driven Assembly of Heterolanthanide (Nd, Er, Yb) Multiple Near-Infrared Emitters journal December 2014
Magnetic interplay between two different lanthanides in a tris-phthalocyaninato complex: a viable synthetic route and detailed investigation in the bulk and on the surface journal January 2015
Design of magnetic coordination complexes for quantum computing journal January 2012
Optimized Slater-type basis sets for the elements 1-118 journal May 2003
Toward heterometallic single-molecule magnets: Synthetic strategy, structures and properties of 3d–4f discrete complexes journal April 2015
Upconversion Luminescent Materials: Advances and Applications journal November 2014
Heterodinuclear Lanthanoid-Containing Polyoxometalates: Stepwise Synthesis and Single-Molecule Magnet Behavior journal September 2013
Programming Heteropolymetallic Lanthanide Helicates: Thermodynamic Recognition of Different Metal Ions Along the Strands journal March 2004
Synthesis of luminescent heterometallic bis-lanthanide complexes via selective, sequential metallation journal January 2006
Lanthanide Contraction within a Series of Asymmetric Dinuclear [Ln 2 ] Complexes journal March 2013
The Lanthanide Contraction Revisited journal September 2007
Heterodimetallic [LnLn′] Lanthanide Complexes: Toward a Chemical Design of Two-Qubit Molecular Spin Quantum Gates journal August 2014
Controlled preparation of a heterometallic lanthanide complex containing different lanthanides in symmetrical binding pockets journal January 2009
Lanthanide-Sensitized Lanthanide Luminescence:  Terbium-Sensitized Ytterbium Luminescence in a Trinuclear Complex journal September 2003
Discriminating between lanthanide ions: self-assembly of heterodimetallic triple-stranded helicates journal January 2002
Relativistic regular two‐component Hamiltonians journal September 1993
Ln 3 Q 9 as a Molecular Framework for Ion-Size-Driven Assembly of Heterolanthanide (Nd, Er, Yb) Multiple Near-Infrared Emitters journal January 2015
Magnetic interplay between two different lanthanides in a tris-phthalocyaninato complex: a viable synthetic route and detailed investigation in the bulk and on the surface text January 2015

Cited By (4)

Rare earth elements: Mendeleev’s bane, modern marvels journal January 2019
Optimization of Magnetic Relaxation and Isotopic Enrichment in Dimeric Dy III Single-Molecule Magnets : Optimization of Magnetic Relaxation and Isotopic Enrichment in Dimeric Dy journal October 2017
Tailored homo- and hetero- lanthanide porphyrin dimers: a synthetic strategy for integrating multiple spintronic functionalities into a single molecule journal January 2018
Controlled Heterometallic Composition in Linear Trinuclear [LnCeLn] Lanthanide Molecular Assemblies journal October 2019

Linked Research (3)

Similar Records

Guest-, Light- and Thermally-Modulated Spin Crossover in [FeII2] Supramolecular Helicates
Journal Article · Tue May 10 00:00:00 EDT 2016 · Chemistry - A European Journal · OSTI ID:1454490
+2 more
New coordination features; A bridging pyridine and the forced shortest non-covalent distance between two CO32- species
Journal Article · Mon Sep 29 00:00:00 EDT 2014 · Chemical Science · OSTI ID:1454490
+6 more
Synthesis, structure and bonding of actinide disulphide dications in the gas phase
Journal Article · Sun Jan 01 00:00:00 EST 2017 · Physical Chemistry Chemical Physics. PCCP · OSTI ID:1454490
+2 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
coordination chemistry
density functional calculations
functional molecules
lanthanides
supramolecular chemistry