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:
-
- Barcelona Inst. of Science and Technology (BIST) (Spain). Inst. of Chemical Research of Catalonia (ICIQ)
- 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.
- Univ. of Barcelona (Spain). Dept. of Inorganic Chemistry
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
- Spanish National Research Council (CSIC) and the Univ. of Zaragoza (Spain). Aragon Materials Science Institute (ICMA)
- 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.
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
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.
@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}
}
Web of Science
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