skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Conducting Molecular Nanomagnet of Dy III with Partially Charged TCNQ Radicals

Authors:
ORCiD logo [1];  [1];  [1];  [1]; ORCiD logo [1]
  1. Department of Chemistry, Texas A&M University, P.O. Box 30012, College Station TX 77842-3012 USA
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1400625
Grant/Contract Number:
AC02-06CH11357; SC0012582
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Chemistry - A European Journal
Additional Journal Information:
Journal Volume: 23; Journal Issue: 31; Related Information: CHORUS Timestamp: 2017-10-20 15:19:11; Journal ID: ISSN 0947-6539
Publisher:
Wiley Blackwell (John Wiley & Sons)
Country of Publication:
Germany
Language:
English

Citation Formats

Zhang, Xuan, Xie, Haomiao, Ballesteros-Rivas, Maria, Woods, Toby J., and Dunbar, Kim R. Conducting Molecular Nanomagnet of Dy III with Partially Charged TCNQ Radicals. Germany: N. p., 2017. Web. doi:10.1002/chem.201701590.
Zhang, Xuan, Xie, Haomiao, Ballesteros-Rivas, Maria, Woods, Toby J., & Dunbar, Kim R. Conducting Molecular Nanomagnet of Dy III with Partially Charged TCNQ Radicals. Germany. doi:10.1002/chem.201701590.
Zhang, Xuan, Xie, Haomiao, Ballesteros-Rivas, Maria, Woods, Toby J., and Dunbar, Kim R. Wed . "Conducting Molecular Nanomagnet of Dy III with Partially Charged TCNQ Radicals". Germany. doi:10.1002/chem.201701590.
@article{osti_1400625,
title = {Conducting Molecular Nanomagnet of Dy III with Partially Charged TCNQ Radicals},
author = {Zhang, Xuan and Xie, Haomiao and Ballesteros-Rivas, Maria and Woods, Toby J. and Dunbar, Kim R.},
abstractNote = {},
doi = {10.1002/chem.201701590},
journal = {Chemistry - A European Journal},
number = 31,
volume = 23,
place = {Germany},
year = {Wed May 10 00:00:00 EDT 2017},
month = {Wed May 10 00:00:00 EDT 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1002/chem.201701590

Citation Metrics:
Cited by: 2works
Citation information provided by
Web of Science

Save / Share:
  • A series of head-on complexes of lanthanoid containing germanotungstates was isolated from a one pot reaction in an acetate buffer at pH 4.5. This convenient approach brought forward the [{l_brace}Ln(CH{sub 3}COO)GeW{sub 11}O{sub 39}(H{sub 2}O){r_brace}{sub 2}]{sup 12-} (Ln=Eu{sup III}, Gd{sup III}, Tb{sup III}, Dy{sup III}, Ho{sup III}, Er{sup III}, Tm{sup III}, and Yb{sup III}) family with acetate chelators in the rarely observed {mu}{sub 2}: {eta}{sup 2}-{eta}{sup 1} mode. All compounds were structurally characterized using various solid state analytics, such as single crystal X-ray diffraction, FT-IR spectroscopy, and thermogravimetric analysis. The isostructural polyanions crystallize in the monoclinic system (S.G. P2{sub 1}/c). Temperature-dependentmore » magnetic susceptibility measurements were performed on the Gd{sup III}-complex which exhibits near perfect Curie-type behavior. -- Graphical abstract: A new series of acetate-chelated lanthanoid containing germanotungstates [{l_brace}Ln(CH{sub 3}COO)GeW{sub 11}O{sub 39}(H{sub 2}O){r_brace}{sub 2}]{sup 12-} (Ln=Eu to Yb) is available from a convenient one-pot reaction. The influence of the lanthanide contraction on the structural properties is discussed and the magnetic properties of the Gd-representative are investigated in detail. Display Omitted Research Highlights: {yields}Lanthanoid containing germanotungstates with acetate chelators in {mu}{sub 2} : {eta}{sup 2}-{eta}{sup 1} mode. {yields}Lanthanoid contraction in [{l_brace}Ln(CH{sub 3}COO)GeW{sub 11}O{sub 39}(H{sub 2}O){r_brace}{sub 2}]{sup 12-} (Ln=Eu{sup III}-Yb{sup III}). {yields}Facile one-pot synthesis of the lanthanoid containing germanotungstate series.« less
  • The charge-transfer reaction between trimethyleneferrocene (Fc(CH/sub 2/)/sub 3/) and 7,7,8,8-tetracyano-p-quinodimethane (TCNQ) results in a 1:2 salt of composition (Fe(C/sub 5/H/sub 4/)/sub 2/(CH/sub 2/)/sub 3//sup +/.)(TCNQ)/sub 2//sup -/.). The crystal and molecular structures of this substance have been determined by single-crystal x-ray diffraction. The complex crystallizes as block plates in the centrosymmetric space group C2/c with the unit cell constants of a = 13.608 (1) A, b = 7.738 (1) A, c = 28.788 (3) A, ..beta.. = 94.336 (8)/sup 0/, V = 3022.66 A/sup 3/, and Z = 4. The structure was solved by a combination of direct methods, Fourier,more » and full-matrix least-squares refinement techniques. A final R/sub F/ = 0.049 was obtained for 2328 reflections where F/sub 0//sup 2/ > sigma(F/sub 0//sup 2/). The structure consists of segregated stacks of ((TCNQ)/sub 2//sup -/.) dimers and trimethyleneferrocenium (Fc(CH/sub 2/)/sub 3//sup +/.) ions, respectively. The stacking distance between the TCNQ/sup 1/2-/ planes of each dimer is 3.162 (5) A, while the distance between dimers is 3.423 (10) A. The ((TCNQ)/sub 2//sup -/.) dimers form stacks which are inclined along the b axis, while the (Fc(CH/sub 2/)/sub 3//sup +/.) ions are aligned along the a axis and rotated 45/sup 0/ about the b axis. The sterically hindering trimethylene bridge causes the C/sub 5/ planes of the (Fe(CH/sub 2/)/sub 3//sup +/.) ion to be tilted at an angle of 13.7 (9)/sup 0/ with respect to each other. This amount is significantly greater than the ring tilt observed for other nonoxidized ferrocenes containing three-membered bridges. The bridging carbon atoms between the rings exhibit disorder. The bond distances of the exocyclic carbon-carbon bonds of the ((TCNQ)/sub 2//sup -/.) ion are 1.390 (3) and 1.394 (4) A, which are consistent with a charge transfer of 0.5 e/TCNQ.« less
  • This salt belongs to the monoclinic space group P2/sub 1//c/sub 1/((a = 9.7076 (12), b = 12.2113 (17), c = 23.5849 (36)); ..beta.. = 95.012 (2)/sup 0/; Z = 4; and rho = 1.265 gcm/sup -3/. The structure was determined by a combination of Patterson, direct methods, Fourier, and least-squares refinement techniques to an R/sub f/ = 0.058 for the 3042 independent observable reflections from a total of 3667 reflections collected on an automatic diffractometer. The crystalline lattice consists of isolated dimeric units of Fe(C/sub 5/Me/sub 5/)/sub 2//TCNQ/TCNQ/Fe(C/sub 5/Me/sub 5/)/sub 2/ A:B:B:A composition. The molecular structure is illustrated and discussed.more » The magnetic susceptibility of powder samples obeys the Curie expression, i.e. chi(T) = 0.81 BM. This is in accord with values obtained for other ferrocenium salts, and suggests very little magnetic coupling between the intradimer S = 1/2 Fe(III) separated by 14 A. The (TCNQ)/sub 2//sup 2 -/ dimer is strongly antiferromagnetically coupled.« less
  • The charge-transfer reaction of decamethylferrocene, Fe(C/sub 5/Me/sub 5/)/sub 2/, Fc*, and 7,7,8,8-tetracyano-p-quinodimethane, TCNQ, has been characterized. Three major reaction products of varying stoichiometry, conductivity, and magnetism are formed: a 1-D metamagnetic 1:1 salt, (Fc*)/sup +/(TCNQ)/sup -/; a paramagnetic (Fc*)/sup 2/ /sup +/(TCNQ)/sup 22 -/; 1:1; dimeric salt, (Fc*)/sup 2/ /sup +/(TCNQ)/sup 22 -/; and a conducting 1:2 salt of (Fc*) /sup +/(TCNQ)/sup 2 -/ composition. The crystal and molecular structures of the 1:1 paramagnetic dimeric and metamagnetic one-dimensional salts were solved. The ions in the dimeric phase crystallize in the centrosymmetric monoclinic space group P2/sub 1//c with a = 9.708more » (1) A, b = 12.211 (2) A, c = 23.585 (4) A, ..beta.. = 95.01 (1)/sup 0/, Z = 4, and R = 0.058 for 3665 independent reflections. The magnetic susceptibility of powder samples of (Fc*)/sup 2/ /sup +/(TCNQ/sub 2/)/sub 2//sup 2 -/ obeys the Curie expression above 1.5 K suggesting very little magnetic coupling between the intradimer S = 1/2 Fe(III)'s which are separated by approx.14 A. The (TCNQ)/sub 2//sup 2 -/ dimer is strongly antiferromagnetically coupled. Ions in the linear chain metamagnetic phase crystallize in the centrosymmetric triclinic space group P1 vector. The unit cell at -106 /sup 0/C is a = 8.635 (4) A, b = 9.384 (6) A, c = 10.635 (9) A; ..cap alpha.. = 116.76 (5)/sup 0/, ..beta.. = 112.58 (5)/sup 0/; ..gamma.. = 72.49 (4)/sup 0/, V = 701.8 A/sup 3/, Z = 1, and R/sub w/ = 0.060 for 1156 reflections. The one-dimensional phase exhibits metamagnetic properties with a Neel temperature of 2.55 K. The intrachain Fe/sup III/-Fe/sup III/separation is 10.540 A. The calculated structure and scaled vibrational frequencies are in excellent agreement with the observed values.« less