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Title: Homoleptic versus Heteroleptic Formation of Mononuclear Fe(II) Complexes with Tris-Imine Ligands

Abstract

In this paper, we show a marked tendency of Fe(II) to form heteroleptic [Fe(L)(L')](ClO4)2 complexes from pairs of chelating tris-imine 3bpp, tpy, or 2bbp ligands. New synthetic avenues for spin crossover research become thus available, here illustrated with three new heteroleptic compounds with differing magnetic behaviors: [Fe(H4L1)(Cl-tpy)](ClO4)2 ·C3H6O (1), [Fe(H2L3)(Me3bpp)](ClO4)2 ·C3H6O (2), [Fe(H4L1)(2bbp)](ClO4)2 ·3C3H6O (3). Structural studies demonstrate that 1 is in the low-spin (LS) state up to 350 K, while complexes 2 and 3 are, by contrast, in the high-spin (HS) state down to 2 K, as corroborated through magnetic susceptibility measurements. Upon exposure to the atmosphere, the latter exhibits the release of three molecules of acetone per complex, turning into the solvent-free analogue [Fe(H4L1)(2bbp)](ClO4)2 (3a), through a single-crystal-to-single-crystal transformation. Lastly, this guest extrusion process is accompanied by a spin switch, from HS to LS.

Authors:
 [1];  [2];  [1];  [3];  [4];  [5];  [1]
  1. University of Barcelona (Spain). Department of Inorganic Chemistry
  2. University of Barcelona (Spain). Department of Inorganic Chemistry; CSIC and University of Zaragoza (Spain). Institute of Materials Science of Aragon (ICMA)
  3. CNRS-Université de Rennes (France). Institut des Sciences Chimiques de Rennes
  4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  5. CSIC and University of Zaragoza (Spain). Institute of Materials Science of Aragon (ICMA)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1439199
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Inorganic Chemistry
Additional Journal Information:
Journal Volume: 55; Journal Issue: 9; Related Information: © 2016 American Chemical Society.; Journal ID: ISSN 0020-1669
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Barrios, Leoni A., Bartual-Murgui, Carlos, Peyrecave-Lleixa, Eugenia, Le Guennic, Boris, Teat, Simon J., Roubeau, Olivier, and Aromi, Guillem. Homoleptic versus Heteroleptic Formation of Mononuclear Fe(II) Complexes with Tris-Imine Ligands. United States: N. p., 2016. Web. https://doi.org/10.1021/acs.inorgchem.5b02058.
Barrios, Leoni A., Bartual-Murgui, Carlos, Peyrecave-Lleixa, Eugenia, Le Guennic, Boris, Teat, Simon J., Roubeau, Olivier, & Aromi, Guillem. Homoleptic versus Heteroleptic Formation of Mononuclear Fe(II) Complexes with Tris-Imine Ligands. United States. https://doi.org/10.1021/acs.inorgchem.5b02058
Barrios, Leoni A., Bartual-Murgui, Carlos, Peyrecave-Lleixa, Eugenia, Le Guennic, Boris, Teat, Simon J., Roubeau, Olivier, and Aromi, Guillem. Wed . "Homoleptic versus Heteroleptic Formation of Mononuclear Fe(II) Complexes with Tris-Imine Ligands". United States. https://doi.org/10.1021/acs.inorgchem.5b02058. https://www.osti.gov/servlets/purl/1439199.
@article{osti_1439199,
title = {Homoleptic versus Heteroleptic Formation of Mononuclear Fe(II) Complexes with Tris-Imine Ligands},
author = {Barrios, Leoni A. and Bartual-Murgui, Carlos and Peyrecave-Lleixa, Eugenia and Le Guennic, Boris and Teat, Simon J. and Roubeau, Olivier and Aromi, Guillem},
abstractNote = {In this paper, we show a marked tendency of Fe(II) to form heteroleptic [Fe(L)(L')](ClO4)2 complexes from pairs of chelating tris-imine 3bpp, tpy, or 2bbp ligands. New synthetic avenues for spin crossover research become thus available, here illustrated with three new heteroleptic compounds with differing magnetic behaviors: [Fe(H4L1)(Cl-tpy)](ClO4)2 ·C3H6O (1), [Fe(H2L3)(Me3bpp)](ClO4)2 ·C3H6O (2), [Fe(H4L1)(2bbp)](ClO4)2 ·3C3H6O (3). Structural studies demonstrate that 1 is in the low-spin (LS) state up to 350 K, while complexes 2 and 3 are, by contrast, in the high-spin (HS) state down to 2 K, as corroborated through magnetic susceptibility measurements. Upon exposure to the atmosphere, the latter exhibits the release of three molecules of acetone per complex, turning into the solvent-free analogue [Fe(H4L1)(2bbp)](ClO4)2 (3a), through a single-crystal-to-single-crystal transformation. Lastly, this guest extrusion process is accompanied by a spin switch, from HS to LS.},
doi = {10.1021/acs.inorgchem.5b02058},
journal = {Inorganic Chemistry},
number = 9,
volume = 55,
place = {United States},
year = {2016},
month = {4}
}

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Cited by: 7 works
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Figures / Tables:

Figure 1 Figure 1: Ligands employed in this work. tpy, 2,6-bis- (pyridine-2-yl)-pyridine; Cl-tpy, 2,6-bis-(pyridine-2-yl)-4- chloro-pyridine; 3bpp, 2,6-bis(pyrazol-3-yl)-pyridine; Me3bpp, 2,6-bis(1-methylpyrazol-3-yl)-pyridine; 2bbp, 2,6-bis(2- benzimidazolyl)-pyridine; H4L1, 2,6-bis(5-(2-hydroxyphenyl)- pyrazol-3-yl)-pyridine; H2L2, 2,6-bis(5-(2-methoxyphenyl)- pyrazol-3-yl)-pyridine and H2L3, 2,6-bis(5-naphthyl-pyrazol-3- yl)-pyridine.

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