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

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

Abstract

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.

Authors:
 [1];  [2];  [3];  [3];  [3];  [4];  [5];  [6]; ORCiD logo [3]
+ Show Author Affiliations
  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
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
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)
OSTI Identifier:
1454490
Alternate Identifier(s):
OSTI ID: 1401274
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
Resource Type:
Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 23; Journal Issue: 21; Related Information: 2017 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim; Journal ID: ISSN 0947-6539
Publisher:
ChemPubSoc Europe
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; coordination chemistry; density functional calculations; functional molecules; lanthanides; supramolecular chemistry

Citation Formats

Gonzalez-Fabra, Joan, Bandeira, Nuno A. G., Velasco, Veronica, Barrios, Leoni A., Aguila, David, Teat, Simon J., Roubeau, Olivier, Bo, Carles, and Aromi, Guillem. Thermodynamic Stability of Heterodimetallic [LnLn'] Complexes: Synthesis and DFT Studies. United States: N. p., 2017. Web. doi:10.1002/chem.201700095.
Copy to clipboard
Gonzalez-Fabra, Joan, Bandeira, Nuno A. G., Velasco, Veronica, Barrios, Leoni A., Aguila, David, Teat, Simon J., Roubeau, Olivier, Bo, Carles, & Aromi, Guillem. Thermodynamic Stability of Heterodimetallic [LnLn'] Complexes: Synthesis and DFT Studies. United States. https://doi.org/10.1002/chem.201700095
Copy to clipboard
Gonzalez-Fabra, Joan, Bandeira, Nuno A. G., Velasco, Veronica, Barrios, Leoni A., Aguila, David, Teat, Simon J., Roubeau, Olivier, Bo, Carles, and Aromi, Guillem. Mon . "Thermodynamic Stability of Heterodimetallic [LnLn'] Complexes: Synthesis and DFT Studies". United States. https://doi.org/10.1002/chem.201700095. https://www.osti.gov/servlets/purl/1454490.
Copy to clipboard
@article{osti_1454490,
title = {Thermodynamic Stability of Heterodimetallic [LnLn'] Complexes: Synthesis and DFT Studies},
author = {Gonzalez-Fabra, Joan and Bandeira, Nuno A. G. and Velasco, Veronica and Barrios, Leoni A. and Aguila, David and Teat, Simon J. and Roubeau, Olivier and Bo, Carles and Aromi, Guillem},
abstractNote = {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.},
doi = {10.1002/chem.201700095},
journal = {Chemistry - A European Journal},
number = 21,
volume = 23,
place = {United States},
year = {Mon Mar 27 00:00:00 EDT 2017},
month = {Mon Mar 27 00:00:00 EDT 2017}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1002/chem.201700095
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 19 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Heterometallic 3d–4f single-molecule magnets
journal, January 2015

  • Rosado Piquer, Lidia; Sañudo, E. Carolina
  • Dalton Transactions, Vol. 44, Issue 19
  • DOI: 10.1039/C5DT00549C

Synthesis and characterization of dinuclear heterometallic lanthanide complexes exhibiting MRI and luminescence response
journal, January 2010

  • Mamedov, Ilgar; Parac-Vogt, Tatjana N.; Logothetis, Nikos K.
  • Dalton Transactions, Vol. 39, Issue 24
  • DOI: 10.1039/b925556g

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

  • Lewis, David J.; Glover, Peter B.; Solomons, Melissa C.
  • Journal of the American Chemical Society, Vol. 133, Issue 4
  • DOI: 10.1021/ja109157g

Managing the Computational Chemistry Big Data Problem: The ioChem-BD Platform
journal, December 2014

  • Álvarez-Moreno, M.; de Graaf, C.; López, N.
  • Journal of Chemical Information and Modeling, Vol. 55, Issue 1
  • DOI: 10.1021/ci500593j

3d−4f Combined Chemistry: Synthetic Strategies and Magnetic Properties
journal, April 2009

  • Andruh, Marius; Costes, Jean-Pierre; Diaz, Carmen
  • Inorganic Chemistry, Vol. 48, Issue 8
  • DOI: 10.1021/ic801027q

Self-assembly between dicarboxylate ions and a binuclear europium complex: formation of stable adducts and heterometallic lanthanide complexes
journal, January 2011

  • Tilney, James A.; Sørensen, Thomas Just; Burton-Pye, Benjamin P.
  • Dalton Transactions, Vol. 40, Issue 45
  • DOI: 10.1039/c1dt11103e

Understanding, Controlling and Programming Cooperativity in Self-Assembled Polynuclear Complexes in Solution
journal, November 2009

  • Riis-Johannessen, Thomas; Dalla Favera, Natalia; Todorova, Tanya K.
  • Chemistry - A European Journal, Vol. 15, Issue 46
  • DOI: 10.1002/chem.200900904

Synthesis and Properties of a Family of Unsymmetric Dinuclear Complexes of Ln III (Ln = Eu, Gd, Tb)
journal, August 2010

  • Aguilà, David; Barrios, Leoní A.; Luis, Fernando
  • Inorganic Chemistry, Vol. 49, Issue 15
  • DOI: 10.1021/ic1008285

Recent advances in dysprosium-based single molecule magnets: Structural overview and synthetic strategies
journal, June 2013

  • Zhang, Peng; Guo, Yun-Nan; Tang, Jinkui
  • Coordination Chemistry Reviews, Vol. 257, Issue 11-12
  • DOI: 10.1016/j.ccr.2013.01.012

Synthesis and Spectroscopic Studies on Azo-Dye Derivatives of Polymetallic Lanthanide Complexes: Using Diazotization to Link Metal Complexes Together
journal, July 2009

  • Placidi, Matteo P.; Villaraza, Aaron Joseph L.; Natrajan, Louise S.
  • Journal of the American Chemical Society, Vol. 131, Issue 29
  • DOI: 10.1021/ja904362f

SHELXT – Integrated space-group and crystal-structure determination
journal, January 2015

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations and Advances, Vol. 71, Issue 1, p. 3-8
  • DOI: 10.1107/S2053273314026370

Supramolecular Recognition of Heteropairs of Lanthanide Ions:  A Step toward Self-Assembled Bifunctional Probes
journal, January 2004

  • André, Nicolas; Jensen, Thomas B.; Scopelliti, Rosario
  • Inorganic Chemistry, Vol. 43, Issue 2
  • DOI: 10.1021/ic0351996

A multicenter numerical integration scheme for polyatomic molecules
journal, February 1988

  • Becke, A. D.
  • The Journal of Chemical Physics, Vol. 88, Issue 4
  • DOI: 10.1063/1.454033

Magnetic lanthanide–transition-metal organic–inorganic hybrid materials: From discrete clusters to extended frameworks
journal, December 2009

  • Huang, You-Gui; Jiang, Fei-Long; Hong, Mao-Chun
  • Coordination Chemistry Reviews, Vol. 253, Issue 23-24
  • DOI: 10.1016/j.ccr.2009.05.007

A Long Journey in Lanthanide Chemistry: From Fundamental Crystallogenesis Studies to Commercial Anticounterfeiting Taggants
journal, April 2016

  • Guillou, Olivier; Daiguebonne, Carole; Calvez, Guillaume
  • Accounts of Chemical Research, Vol. 49, Issue 5
  • DOI: 10.1021/acs.accounts.6b00058

Structure-Based Description of a Step-by-Step Synthesis of Homo- and Heterodinuclear (4f, 4f ‘) Lanthanide Complexes
journal, October 2003

  • Costes, Jean-Pierre; Dahan, Françoise; Nicodème, Franck
  • Inorganic Chemistry, Vol. 42, Issue 20
  • DOI: 10.1021/ic034564q

A short history of SHELX
journal, December 2007

  • Sheldrick, George M.
  • Acta Crystallographica Section A Foundations of Crystallography, Vol. 64, Issue 1, p. 112-122
  • DOI: 10.1107/S0108767307043930

Tuneable Intramolecular Intermetallic Interactions as a New Tool for Programming Linear Heterometallic 4f−4f Complexes
journal, October 2007

  • Dalla-Favera, Natalia; Hamacek, Josef; Borkovec, Michal
  • Inorganic Chemistry, Vol. 46, Issue 22
  • DOI: 10.1021/ic701308h

Revised Ionic Radii of Lanthanoid(III) Ions in Aqueous Solution
journal, May 2011

  • D’Angelo, Paola; Zitolo, Andrea; Migliorati, Valentina
  • Inorganic Chemistry, Vol. 50, Issue 10
  • DOI: 10.1021/ic200260r

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

  • Li, Yi-Ming; Kuang, Wei-Wei; Zhu, Li-Li
  • European Journal of Inorganic Chemistry, Vol. 2016, Issue 31
  • DOI: 10.1002/ejic.201600556

Rare-Earth Metal Oxo/Hydroxo Clusters - Synthesis, Structures, and Applications
journal, January 2016

  • Wagner, Anna T.; Roesky, Peter W.
  • European Journal of Inorganic Chemistry, Vol. 2016, Issue 6
  • DOI: 10.1002/ejic.201501281

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

  • Artizzu, Flavia; Quochi, Francesco; Marchiò, Luciano
  • Chemistry - A European Journal, Vol. 21, Issue 10
  • DOI: 10.1002/chem.201405634

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

  • Lan, Yanhua; Klyatskaya, Svetlana; Ruben, Mario
  • Journal of Materials Chemistry C, Vol. 3, Issue 38
  • DOI: 10.1039/C5TC02011E

Design of magnetic coordination complexes for quantum computing
journal, January 2012

  • Aromí, Guillem; Aguilà, David; Gamez, Patrick
  • Chem. Soc. Rev., Vol. 41, Issue 2
  • DOI: 10.1039/C1CS15115K

Optimized Slater-type basis sets for the elements 1-118
journal, May 2003

  • Van Lenthe, E.; Baerends, E. J.
  • Journal of Computational Chemistry, Vol. 24, Issue 9
  • DOI: 10.1002/jcc.10255

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

  • Zhou, Jing; Liu, Qian; Feng, Wei
  • Chemical Reviews, Vol. 115, Issue 1
  • DOI: 10.1021/cr400478f

Heterodinuclear Lanthanoid-Containing Polyoxometalates: Stepwise Synthesis and Single-Molecule Magnet Behavior
journal, September 2013

  • Sato, Rinta; Suzuki, Kosuke; Sugawa, Midori
  • Chemistry - A European Journal, Vol. 19, Issue 39
  • DOI: 10.1002/chem.201302596

Programming Heteropolymetallic Lanthanide Helicates: Thermodynamic Recognition of Different Metal Ions Along the Strands
journal, March 2004

  • Floquet, Sébastien; Borkovec, Michal; Bernardinelli, Gérald
  • Chemistry - A European Journal, Vol. 10, Issue 5
  • DOI: 10.1002/chem.200305498

Synthesis of luminescent heterometallic bis-lanthanide complexes via selective, sequential metallation
journal, January 2006

  • Tremblay, Matthew S.; Sames, Dalibor
  • Chemical Communications, Issue 39
  • DOI: 10.1039/b607949k

Lanthanide Contraction within a Series of Asymmetric Dinuclear [Ln 2 ] Complexes
journal, March 2013

  • Aguilà, David; Barrios, Leoní A.; Velasco, Verónica
  • Chemistry - A European Journal, Vol. 19, Issue 19
  • DOI: 10.1002/chem.201204451

The Lanthanide Contraction Revisited
journal, September 2007

  • Seitz, Michael; Oliver, Allen G.; Raymond, Kenneth N.
  • Journal of the American Chemical Society, Vol. 129, Issue 36
  • DOI: 10.1021/ja072750f

Heterodimetallic [LnLn′] Lanthanide Complexes: Toward a Chemical Design of Two-Qubit Molecular Spin Quantum Gates
journal, August 2014

  • Aguilà, David; Barrios, Leoní A.; Velasco, Verónica
  • Journal of the American Chemical Society, Vol. 136, Issue 40
  • DOI: 10.1021/ja507809w

Controlled preparation of a heterometallic lanthanide complex containing different lanthanides in symmetrical binding pockets
journal, January 2009

  • Natrajan, Louise S.; Villaraza, Aaron Joseph L.; Kenwright, Alan M.
  • Chemical Communications, Issue 40
  • DOI: 10.1039/b913702e

Lanthanide-Sensitized Lanthanide Luminescence:  Terbium-Sensitized Ytterbium Luminescence in a Trinuclear Complex
journal, September 2003

  • Faulkner, Stephen; Pope, Simon J. A.
  • Journal of the American Chemical Society, Vol. 125, Issue 35
  • DOI: 10.1021/ja035634v

Discriminating between lanthanide ions: self-assembly of heterodimetallic triple-stranded helicates
journal, January 2002

  • André, Nicolas; Scopelliti, Rosario; Hopfgartner, Gérard
  • Chemical Communications, Issue 3
  • DOI: 10.1039/b109065h

Relativistic regular two‐component Hamiltonians
journal, September 1993

  • Lenthe, E. van; Baerends, E. J.; Snijders, J. G.
  • The Journal of Chemical Physics, Vol. 99, Issue 6
  • DOI: 10.1063/1.466059

Lanthanides and Actinides in Molecular Magnetism
book, January 2015

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

  • Artizzu, Flavia; Quochi, Francesco; Marchiò, Luciano
  • Chemistry - A European Journal, Vol. 21, Issue 10
  • DOI: 10.1002/chem.201406660
    Sort by:
    [ × clear filter / sort ]

    Works referencing / citing this record:

    Rare earth elements: Mendeleev’s bane, modern marvels
    journal, January 2019

    Controlled Heterometallic Composition in Linear Trinuclear [LnCeLn] Lanthanide Molecular Assemblies
    journal, October 2019

    • Velasco, Verónica; Barrios, Leoní A.; Schütze, Mike
    • Chemistry – A European Journal, Vol. 25, Issue 67
    • DOI: 10.1002/chem.201903829
      Sort by:
      [ × clear filter / sort ]

      Similar Records in DOE PAGES and OSTI.GOV collections:

      Other research related to this record: