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Title: 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:
 [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]
+ Show Author Affiliations
  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.
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.
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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
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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.
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@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}
}
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Journal Article:
Free Publicly Available Full Text
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https://doi.org/10.1088/1361-648x/ab468c
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Figures / Tables:

Figure 1 Figure 1: The experimental Raman spectra of the spin-crossover molecule [Fe(H2B(pz)2)2(bipy)] (c-black), with the zwitterionic p-benzoquinonemonoimine C6H2(···NH2)2(···O)2, (a-red), with the admixture of the two, in the molar ratio of 1:2, showing Raman features of each component (b-green).
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