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

The solid-state and solution configurations of the heterodimetallic complexes (Hpy)[LaEr(HL) 3(NO 3)(py)(H 2O)] (1), (Hpy)[CeEr(HL) 3(NO 3)(py)(H 2O)] (2), (Hpy)[CeGd(HL) 3(NO 3)(py)(H 2O)] (3), (Hpy)[PrSm(HL) 3(NO 3)(py)(H 2O)] (4), and (Hpy) 2[LaYb(HL) 3(NO 3)(H 2O)](NO 3) (5), in which H 3L 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]
  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:
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
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
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); European Research Council (ERC); Ministry of Economy and Enterprise (MINECO) (Spain); European Commission (EC); Foundation for Science and Technology (FCT) (Portugal)
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
OSTI Identifier:
1454490
Alternate Identifier(s):
OSTI ID: 1401274

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., 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. 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, and Aromi, Guillem. 2017. "Thermodynamic Stability of Heterodimetallic [LnLn'] Complexes: Synthesis and DFT Studies". United States. doi: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 = {2017},
month = {3}
}

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SHELXT � Integrated space-group and crystal-structure determination
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