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Title: Manipulation of the molecular spin crossover transition of Fe(H2B(pz)2)2(bipy) by addition of polar molecules

Journal Article · · Journal of Physics. Condensed Matter
 [1]; ORCiD logo [1]; ORCiD logo [2];  [3]; ORCiD logo [4];  [5];  [6];  [1]; ORCiD logo [7];  [7];  [8]; ORCiD logo [9]; ORCiD logo [1]
  1. Univ. of Nebraska, Lincoln, NE (United States). Dept. of Physics and Astronomy
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
  3. Univ. of Strasbourg (France); Univ. Paul Sabatier, Toulouse (France)
  4. Univ. of Strasbourg (France)
  5. Univ. of Nebraska, Lincoln, NE (United States). Dept. of Chemistry
  6. Univ. of Nebraska, Lincoln, NE (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
  7. Univ. of Nebraska, Lincoln, NE (United States). Dept. of Food Science and Technology
  8. Univ. de Strasbourg (France)
  9. Univ. Bayreuth (Germany). Physikalisches Inst.

In this paper, the addition of various dipolar molecules is shown to affect the temperature dependence of the spin state occupancy of the much studied spin crossover Fe(II) complex, [Fe{H2B(pz)2}2(bipy)] (pz = pyrazol-1-yl, bipy = 2,2'-bipyridine). Specifically, the addition of benzimidazole results in a re-entrant spin crossover transition, i.e. the spin state starts in the mostly low spin state, then high spin state occupancy increases, and finally the high spin state occupancy decreases with increasing temperature. This behavior contrasts with that observed when the highly polar ρ-benzoquinonemonoimine zwitterion C6H2(...NH2)2(...O)2 was mixed with [Fe{H2B(pz)2}2(bipy)], which resulted in locking [Fe{H2B(pz)2}2(bipy)] largely into a low spin state while addition of the ethyl derivative C6H2(...NHC2H5)2(...O)2 did not appear to perturb the spin crossover transition of [Fe{H2B(pz)2}2(bipy)].

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Agence Nationale de la Recherche
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1635179
Alternate ID(s):
OSTI ID: 23015729
Journal Information:
Journal of Physics. Condensed Matter, Journal Name: Journal of Physics. Condensed Matter Journal Issue: 3 Vol. 32; ISSN 0953-8984
Publisher:
IOP PublishingCopyright Statement
Country of Publication:
United States
Language:
English

References (22)

Electronic Structure of a Spin Crossover Molecular Adsorbate journal October 2012
The possible phase diagrams for the transverse Ising model with temperature-dependent parameters journal June 2014
A 6π + 6π Potentially Antiaromatic Zwitterion Preferred to a Quinoidal Structure:  Its Reactivity Toward Organic and Inorganic Reagents journal October 2003
Structure and Proton-Transfer Mechanism in One-Dimensional Chains of Benzimidazoles journal January 2016
Temperature- and Light-Induced Spin Crossover Observed by X-ray Spectroscopy on Isolated Fe(II) Complexes on Gold journal April 2013
Hydrogen Bonds NH···N in Compressed Benzimidazole Polymorphs journal December 2012
Thermal and Optical Switching of Molecular Spin States in the {[FeL[H 2 B(pz) 2 ] 2 } Spin-Crossover System (L = bpy, phen) journal April 2002
Tunable N-substitution in Zwitterionic Benzoquinonemonoimine Derivatives: Metal Coordination, Tandemlike Synthesis of Zwitterionic Metal Complexes, and Supramolecular Structures journal December 2005
Spin Crossover in Novel Dihydrobis(1-pyrazolyl)borate [H 2 B(pz) 2 ]-Containing Iron(II) Complexes. Synthesis, X-ray Structure, and Magnetic Properties of [FeL{H 2 B(pz) 2 } 2 ] (L = 1,10-Phenanthroline and 2,2‘-Bipyridine) journal July 1997
Modification of Molecular Spin Crossover in Ultrathin Films journal March 2013
Complexities in the Molecular Spin Crossover Transition journal June 2015
Locking and Unlocking the Molecular Spin Crossover Transition journal August 2017
Spin crossover materials evaporated under clean high vacuum and ultra-high vacuum conditions: from thin films to single molecules journal January 2012
Investigating global phase diagrams (GPDs) with reentrant transition behavior journal July 2018
Magnetic phase diagram and magnetic pairing in doped La 2 CuO 4 journal March 1988
Theory of the reentrant transition in a lamellar antiferromagnet: doped La2CuO4 journal February 1990
Indications of magnetic coupling effects in spin cross-over molecular thin films journal January 2018
Performance Characteristics of Beamline 6.3.1 from 200 eV to 2000 eV at the Advanced Light Source
  • Nachimuthu, P.
  • SYNCHROTRON RADIATION INSTRUMENTATION: Eighth International Conference on Synchrotron Radiation Instrumentation, AIP Conference Proceedings https://doi.org/10.1063/1.1757832
conference January 2004
Surface-induced spin state locking of the [Fe(H 2 B(pz) 2 ) 2 (bipy)] spin crossover complex journal April 2016
Reactions of Amines with Zwitterionic Quinoneimines: Synthesis of New Anionic and Zwitterionic Quinonoids journal July 2009
Unprecedented zwitterion in quinonoid chemistryElectronic supplementary information (ESI) available: spectroscopic data for 4 and 6 and an ORTEP view of the structure of 4. See http://www.rsc.org/suppdata/cc/b1/b107828n/. journal January 2002
Excited Spin-State Trapping in Spin Crossover Complexes on Ferroelectric Substrates journal March 2018