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

Journal Article · · Inorganic Chemistry
 [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)
+ Show Author Affiliations

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.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1439199
Journal Information:
Inorganic Chemistry, Vol. 55, Issue 9; Related Information: © 2016 American Chemical Society.; ISSN 0020-1669
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 25 works
Citation information provided by
Web of Science

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Cited By (11)

Solvent Effects on the Spin-Transition in a Series of Fe(II) Dinuclear Triple Helicate Compounds journal September 2018
Designed intramolecular blocking of the spin crossover of an Fe( ii ) complex journal January 2016
A Sequential Method to Prepare Polymorphs and Solvatomorphs of [Fe(1,3-bpp) 2 ](ClO 4 ) 2 ⋅ n H 2 O ( n =0, 1, 2) with Varying Spin-Crossover Behaviour journal August 2016
Homoleptic versus heteroleptic trinuclear systems with mixed l -cysteinate and d -penicillaminate regulated by a diphosphine linker journal January 2020
Excited‐State Kinetics of an Air‐Stable Cyclometalated Iron(II) Complex journal June 2019
Iron(II) complexes with N 2 O 2 coordinating Schiff base-like equatorial ligand and 1,2-bis(pyridin-2-ylethynyl)benzene as axial pincer ligand journal September 2019
A probe of steric ligand substituent effects on the spin crossover of Fe( ii ) complexes journal January 2017
Intramolecular Spin State Locking in Iron(II) 2,6-Di(pyrazol-3-yl)pyridine Complexes by Phenyl Groups: An Experimental Study journal October 2018
Towards the Molecular Design of Spin‐Crossover Complexes of 2,6‐Bis(pyrazol‐3‐yl)pyridines journal March 2020
Step-by-step: uncommon SCSC transformation accompanied by stepwise change in the binding of a particular ligand within a mononuclear complex upon stepwise desolvation journal January 2020
Lattice-Solvent Effects in the Spin-Crossover of an Fe(II)-Based Material. The Key Role of Intermolecular Interactions between Solvent Molecules journal March 2017

Linked Research (6)

Figures / Tables (7)

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY