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Thermodynamic Stability of Heterodimetallic [LnLn′] Complexes: Synthesis and DFT Studies
Author(s) -
GónzalezFabra Joan,
Bandeira Nuno A. G.,
Velasco Verónica,
Barrios Leoní A.,
Aguilà David,
Teat Simon J.,
Roubeau Olivier,
Bo Carles,
Aromí Guillem
Publication year - 2017
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201700095
Subject(s) - chemistry , crystallography , pyridine , selectivity , molecule , dissociation (chemistry) , metal ions in aqueous solution , metal , crystal structure , solid state , ion , stereochemistry , medicinal chemistry , organic chemistry , catalysis
The solid‐state and solution configurations of the heterodimetallic complexes (Hpy)[LaEr(HL) 3 (NO 3 )(py)(H 2 O)] ( 1 ), (Hpy)[CeEr(HL) 3 (NO 3 )(py)(H 2 O)] ( 2 ), (Hpy)[CeGd(HL) 3 (NO 3 )(py)(H 2 O)] ( 3 ), (Hpy)[PrSm(HL) 3 (NO 3 )(py)(H 2 O)] ( 4 ), and (Hpy) 2 [LaYb(HL) 3 (NO 3 )(H 2 O)](NO 3 ) ( 5 ), in which H 3 L 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.