Synthesis, Crystal Structure and Magnetic Characterization of a Series of Cu-II-Ln(III) Heterometallic [Ln = La, Ce, Pr, Nd and Sm) Metal-Organic Compounds with an Unusual Single Crystal to Single Crystal Phase Transition
Diaz-Gallifa, Pau ; Fabelo, Oscar ; Canadillas-Delgado, Laura ; Pasan, Jorge ; Labrador, Ana LU
; Lloret, Francesc
; Julve, Miguel
and Ruiz-Perez, Catalina
(2013)
In Crystal Growth & Design
13(11).
p.4735-4745
- Abstract
- The synthesis and structural characterization of five Cu(II)-Ln(III) heteronuclear metal-organic frameworks of formula {[Ln(4)Cu(4)(H2O)(26)(bta)(5)]center dot mH(2)O} and {[Ln(4)Cu(4)(H2O)(24)(bta)(5)]center dot pH(2)O} [Ln = La-III (1A/1B), Ce-III (2A/2B), Pr-III (3A/3B), Nd-III (4A/4B) and Sm-III (5A/5B) with m/p = 20 (1A)/16 (1B), 18 (2A)/16 (2B), 14 (3016 (3B), 22 (4A)/16 (4B) and 21 (5A)/14 (5B); H(4)bta =1,2,4,5-benzenetetracarboxylic acid (1-5)] have been performed. These compounds present a single-crystal to single-crystal phase transition from expanded A phases toward the B shrinking networks, which is triggered only in the presence of a dry environment. This phase transition is accompanied by a compression of the... (More)
- The synthesis and structural characterization of five Cu(II)-Ln(III) heteronuclear metal-organic frameworks of formula {[Ln(4)Cu(4)(H2O)(26)(bta)(5)]center dot mH(2)O} and {[Ln(4)Cu(4)(H2O)(24)(bta)(5)]center dot pH(2)O} [Ln = La-III (1A/1B), Ce-III (2A/2B), Pr-III (3A/3B), Nd-III (4A/4B) and Sm-III (5A/5B) with m/p = 20 (1A)/16 (1B), 18 (2A)/16 (2B), 14 (3016 (3B), 22 (4A)/16 (4B) and 21 (5A)/14 (5B); H(4)bta =1,2,4,5-benzenetetracarboxylic acid (1-5)] have been performed. These compounds present a single-crystal to single-crystal phase transition from expanded A phases toward the B shrinking networks, which is triggered only in the presence of a dry environment. This phase transition is accompanied by a compression of the crystallographic b-axis in the range 2.4 to 2.8 angstrom with the consequent decrease of the unit cell volume from 9.5% to 12%. The isomorphous crystal structures of 1A-5A can be described as two crystallographically independent [Cu(II)-Ln(III)] heterometallic dinuclear units which are connected through two crystallographically independent bta(4-) ligands in the ac-plane, leading to 4,4-rectangular grids. These layers are connected along the crystallographic b-axis, through a pillaring bta(4-) group. The phase transition implies a change of the coordination mode of the bta4- pillar from bis-monodentate (1A-5A) to tetrakis-monodentate (1B-5B). Magnetic susceptibility measurements of polycrystalline samples of 1A-5A in the temperature range 2.0-300 K have in common the decrease of the chi T-M product with T which in the case of 1A is due to weak antiferromagnetic interactions between the copper(II) ions through the bta4- skeleton, the Lam cation being diamagnetic [J = -3.5 cm(-1) with the Hamiltonian defined H = -JS(Cu1)center dot S-Cu2,]. For the 2A-5A compounds, the additional exchange interaction between Cu-II and the paramagnetic Ln(II) is masked by the crystal field effects (which partially removes the 2J + 1 degeneracy of the L-2S+1(J) free-ion ground state in zero magnetic field) (2A-5A) and the thermal population of excited free-ion states (5A). (Less)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/4200954
- author
- Diaz-Gallifa, Pau
; Fabelo, Oscar
; Canadillas-Delgado, Laura
; Pasan, Jorge
; Labrador, Ana
LU
; Lloret, Francesc
; Julve, Miguel
and Ruiz-Perez, Catalina
- organization
- publishing date
- 2013
- type
- Contribution to journal
- publication status
- published
- subject
- in
- Crystal Growth & Design
- volume
- 13
- issue
- 11
- pages
- 4735 - 4745
- publisher
- The American Chemical Society (ACS)
- external identifiers
-
- wos:000326775000016
- scopus:84887756910
- ISSN
- 1528-7483
- DOI
- 10.1021/cg4008679
- language
- English
- LU publication?
- yes
- id
- d6f948fd-aa6c-4767-8bb7-085937c2971f (old id 4200954)
- date added to LUP
- 2016-04-01 11:17:21
- date last changed
- 2022-01-26 06:52:27
@article{d6f948fd-aa6c-4767-8bb7-085937c2971f,
abstract = {{The synthesis and structural characterization of five Cu(II)-Ln(III) heteronuclear metal-organic frameworks of formula {[Ln(4)Cu(4)(H2O)(26)(bta)(5)]center dot mH(2)O} and {[Ln(4)Cu(4)(H2O)(24)(bta)(5)]center dot pH(2)O} [Ln = La-III (1A/1B), Ce-III (2A/2B), Pr-III (3A/3B), Nd-III (4A/4B) and Sm-III (5A/5B) with m/p = 20 (1A)/16 (1B), 18 (2A)/16 (2B), 14 (3016 (3B), 22 (4A)/16 (4B) and 21 (5A)/14 (5B); H(4)bta =1,2,4,5-benzenetetracarboxylic acid (1-5)] have been performed. These compounds present a single-crystal to single-crystal phase transition from expanded A phases toward the B shrinking networks, which is triggered only in the presence of a dry environment. This phase transition is accompanied by a compression of the crystallographic b-axis in the range 2.4 to 2.8 angstrom with the consequent decrease of the unit cell volume from 9.5% to 12%. The isomorphous crystal structures of 1A-5A can be described as two crystallographically independent [Cu(II)-Ln(III)] heterometallic dinuclear units which are connected through two crystallographically independent bta(4-) ligands in the ac-plane, leading to 4,4-rectangular grids. These layers are connected along the crystallographic b-axis, through a pillaring bta(4-) group. The phase transition implies a change of the coordination mode of the bta4- pillar from bis-monodentate (1A-5A) to tetrakis-monodentate (1B-5B). Magnetic susceptibility measurements of polycrystalline samples of 1A-5A in the temperature range 2.0-300 K have in common the decrease of the chi T-M product with T which in the case of 1A is due to weak antiferromagnetic interactions between the copper(II) ions through the bta4- skeleton, the Lam cation being diamagnetic [J = -3.5 cm(-1) with the Hamiltonian defined H = -JS(Cu1)center dot S-Cu2,]. For the 2A-5A compounds, the additional exchange interaction between Cu-II and the paramagnetic Ln(II) is masked by the crystal field effects (which partially removes the 2J + 1 degeneracy of the L-2S+1(J) free-ion ground state in zero magnetic field) (2A-5A) and the thermal population of excited free-ion states (5A).}},
author = {{Diaz-Gallifa, Pau and Fabelo, Oscar and Canadillas-Delgado, Laura and Pasan, Jorge and Labrador, Ana and Lloret, Francesc and Julve, Miguel and Ruiz-Perez, Catalina}},
issn = {{1528-7483}},
language = {{eng}},
number = {{11}},
pages = {{4735--4745}},
publisher = {{The American Chemical Society (ACS)}},
series = {{Crystal Growth & Design}},
title = {{Synthesis, Crystal Structure and Magnetic Characterization of a Series of Cu-II-Ln(III) Heterometallic [Ln = La, Ce, Pr, Nd and Sm) Metal-Organic Compounds with an Unusual Single Crystal to Single Crystal Phase Transition}},
url = {{http://dx.doi.org/10.1021/cg4008679}},
doi = {{10.1021/cg4008679}},
volume = {{13}},
year = {{2013}},
}