Manipulation of the molecular spin crossover transition of Fe(H2B(pz)2)2(bipy) by addition of polar molecules
Abstract
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)].
- Authors:
-
- Univ. of Nebraska, Lincoln, NE (United States). Dept. of Physics and Astronomy
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Advanced Light Source (ALS)
- Univ. of Strasbourg (France); Univ. Paul Sabatier, Toulouse (France)
- Univ. of Strasbourg (France)
- Univ. of Nebraska, Lincoln, NE (United States). Dept. of Chemistry
- Univ. of Nebraska, Lincoln, NE (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Molecular Foundry
- Univ. of Nebraska, Lincoln, NE (United States). Dept. of Food Science and Technology
- Univ. de Strasbourg (France)
- Univ. Bayreuth (Germany). Physikalisches Inst.
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); Agence Nationale de la Recherche
- OSTI Identifier:
- 1635179
- Grant/Contract Number:
- AC02-05CH11231; 1565692; 1420645; 11-BS08-06
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physics. Condensed Matter
- Additional Journal Information:
- Journal Volume: 32; Journal Issue: 3; Journal ID: ISSN 0953-8984
- Publisher:
- IOP Publishing
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND SUPERFLUIDITY; spin crossover metal organic molecules, x-ray absorption spectroscopy, dipolar heteromolecular molecular interactions, re-entrant transition
Citation Formats
Costa, Paulo S, Hao, Guanhua, N’Diaye, Alpha T, Routaboul, Lucie, Braunstein, Pierre, Zhang, Xin, Zhang, Jian, Ekanayaka, Thilini K, Shi, Qin-Yin, Schlegel, Vicki, Doudin, Bernard, Enders, Axel, and Dowben, P A. Manipulation of the molecular spin crossover transition of Fe(H2B(pz)2)2(bipy) by addition of polar molecules. United States: N. p., 2019.
Web. doi:10.1088/1361-648x/ab468c.
Costa, Paulo S, Hao, Guanhua, N’Diaye, Alpha T, Routaboul, Lucie, Braunstein, Pierre, Zhang, Xin, Zhang, Jian, Ekanayaka, Thilini K, Shi, Qin-Yin, Schlegel, Vicki, Doudin, Bernard, Enders, Axel, & Dowben, P A. Manipulation of the molecular spin crossover transition of Fe(H2B(pz)2)2(bipy) by addition of polar molecules. United States. https://doi.org/10.1088/1361-648x/ab468c
Costa, Paulo S, Hao, Guanhua, N’Diaye, Alpha T, Routaboul, Lucie, Braunstein, Pierre, Zhang, Xin, Zhang, Jian, Ekanayaka, Thilini K, Shi, Qin-Yin, Schlegel, Vicki, Doudin, Bernard, Enders, Axel, and Dowben, P A. Tue .
"Manipulation of the molecular spin crossover transition of Fe(H2B(pz)2)2(bipy) by addition of polar molecules". United States. https://doi.org/10.1088/1361-648x/ab468c. https://www.osti.gov/servlets/purl/1635179.
@article{osti_1635179,
title = {Manipulation of the molecular spin crossover transition of Fe(H2B(pz)2)2(bipy) by addition of polar molecules},
author = {Costa, Paulo S and Hao, Guanhua and N’Diaye, Alpha T and Routaboul, Lucie and Braunstein, Pierre and Zhang, Xin and Zhang, Jian and Ekanayaka, Thilini K and Shi, Qin-Yin and Schlegel, Vicki and Doudin, Bernard and Enders, Axel and Dowben, P A},
abstractNote = {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)].},
doi = {10.1088/1361-648x/ab468c},
journal = {Journal of Physics. Condensed Matter},
number = 3,
volume = 32,
place = {United States},
year = {2019},
month = {10}
}
Web of Science
Figures / Tables:

Works referenced in this record:
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
- Moliner, Nicolás; Salmon, Lionel; Capes, Laurence
- The Journal of Physical Chemistry B, Vol. 106, Issue 16
The possible phase diagrams for the transverse Ising model with temperature-dependent parameters
journal, June 2014
- Simons, Bayor Jude; Teng, Baohua; Zhou, Shanyu
- Chemical Physics Letters, Vol. 605-606
Excited Spin-State Trapping in Spin Crossover Complexes on Ferroelectric Substrates
journal, March 2018
- Wäckerlin, Christian; Donati, Fabio; Singha, Aparajita
- The Journal of Physical Chemistry C, Vol. 122, Issue 15
Indications of magnetic coupling effects in spin cross-over molecular thin films
journal, January 2018
- Zhang, Xin; N'Diaye, Alpha T.; Jiang, Xuanyuan
- Chemical Communications, Vol. 54, Issue 8
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
- Siri, Olivier; Braunstein, Pierre
- Chemical Communications, Issue 3
Magnetic phase diagram and magnetic pairing in doped
journal, March 1988
- Aharony, Amnon; Birgeneau, R. J.; Coniglio, A.
- Physical Review Letters, Vol. 60, Issue 13
Electronic Structure of a Spin Crossover Molecular Adsorbate
journal, October 2012
- Zhang, Xin; Palamarciuc, Tatiana; Rosa, Patrick
- The Journal of Physical Chemistry C, Vol. 116, Issue 44
Hydrogen Bonds NH···N in Compressed Benzimidazole Polymorphs
journal, December 2012
- Zieliński, Witold; Katrusiak, Andrzej
- Crystal Growth & Design, Vol. 13, Issue 2
Locking and Unlocking the Molecular Spin Crossover Transition
journal, August 2017
- Zhang, Xin; Costa, Paulo S.; Hooper, James
- Advanced Materials, Vol. 29, Issue 39
Tunable N-substitution in Zwitterionic Benzoquinonemonoimine Derivatives: Metal Coordination, Tandemlike Synthesis of Zwitterionic Metal Complexes, and Supramolecular Structures
journal, December 2005
- Yang, Qing-Zheng; Siri, Olivier; Braunstein, Pierre
- Chemistry - A European Journal, Vol. 11, Issue 24
Structure and Proton-Transfer Mechanism in One-Dimensional Chains of Benzimidazoles
journal, January 2016
- Costa, Paulo S.; Miller, Daniel P.; Teeter, Jacob D.
- The Journal of Physical Chemistry C, Vol. 120, Issue 10
Temperature- and Light-Induced Spin Crossover Observed by X-ray Spectroscopy on Isolated Fe(II) Complexes on Gold
journal, April 2013
- Warner, Ben; Oberg, Jenny C.; Gill, Tobias G.
- The Journal of Physical Chemistry Letters, Vol. 4, Issue 9
Theory of the reentrant transition in a lamellar antiferromagnet: doped La2CuO4
journal, February 1990
- Glazman, L. I.; Ioselevich, A. S.
- Zeitschrift f�r Physik B Condensed Matter, Vol. 80, Issue 1
A 6π + 6π Potentially Antiaromatic Zwitterion Preferred to a Quinoidal Structure: Its Reactivity Toward Organic and Inorganic Reagents
journal, October 2003
- Braunstein, Pierre; Siri, Olivier; Taquet, Jean-philippe
- Journal of the American Chemical Society, Vol. 125, Issue 40
Surface-induced spin state locking of the [Fe(H 2 B(pz) 2 ) 2 (bipy)] spin crossover complex
journal, April 2016
- Beniwal, S.; Zhang, X.; Mu, S.
- Journal of Physics: Condensed Matter, Vol. 28, Issue 20
Performance Characteristics of Beamline 6.3.1 from 200 eV to 2000 eV at the Advanced Light Source
conference, January 2004
- Nachimuthu, P.
- SYNCHROTRON RADIATION INSTRUMENTATION: Eighth International Conference on Synchrotron Radiation Instrumentation, AIP Conference Proceedings
Complexities in the Molecular Spin Crossover Transition
journal, June 2015
- Zhang, Xin; Mu, Sai; Chastanet, Guillaume
- The Journal of Physical Chemistry C, Vol. 119, Issue 28
Modification of Molecular Spin Crossover in Ultrathin Films
journal, March 2013
- Pronschinske, Alex; Chen, Yifeng; Lewis, Geoffrey F.
- Nano Letters, Vol. 13, Issue 4
Spin crossover materials evaporated under clean high vacuum and ultra-high vacuum conditions: from thin films to single molecules
journal, January 2012
- Palamarciuc, Tatiana; Oberg, Jenny C.; El Hallak, Fadi
- Journal of Materials Chemistry, Vol. 22, Issue 19
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
- Real, José Antonio; Muñoz, M. Carmen; Faus, Juan
- Inorganic Chemistry, Vol. 36, Issue 14
Reactions of Amines with Zwitterionic Quinoneimines: Synthesis of New Anionic and Zwitterionic Quinonoids
journal, July 2009
- Tamboura, Farba B.; Cazin, Catherine S. J.; Pattacini, Roberto
- European Journal of Organic Chemistry, Vol. 2009, Issue 20
Investigating global phase diagrams (GPDs) with reentrant transition behavior
journal, July 2018
- Bayor, Jude Simons; Teng, Baohua; Wang, Lingli
- PLOS ONE, Vol. 13, Issue 7
Figures / Tables found in this record: