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⁵⁵Mn NMR and Relaxation in Single Crystals of Mn₁₂-Ac and Analogs

Title: ⁵⁵Mn NMR and Relaxation in Single Crystals of Mn₁₂-Ac and Analogs.
Name(s): Harter, Andrew, Ph. D., author
Dalal, Naresh, professor directing dissertation
Brooks, James, outside committee member
Marshall, Alan, committee member
Reyes, Arneil, committee member
Steinbock, Oliver, committee member
Department of Chemistry and Biochemistry, degree granting department
Florida State University, degree granting institution
Type of Resource: text
Genre: Text
Issuance: monographic
Date Issued: 2006
Publisher: Florida State University
Florida State University
Place of Publication: Tallahassee, Florida
Physical Form: computer
online resource
Extent: 1 online resource
Language(s): English
Abstract/Description: This dissertation presents the first single crystal 55Mn NMR characterization of three compounds related to Mn12-acetate [Mn12O12(O2CCH3)16(H2O)4]× 2CH3COOH-4H2O (henceforth Mn12-Ac) that have come to be known as Single-Molecule Magnets (SMMs). This study was undertaken because they exhibit novel phenomena such as quantum mechanical tunneling of their magnetization (QTM), the origin of which is still not fully understood, and also because they have the potential to form elements of magnetic memory storage at the molecular dimensions. The investigations herein involve studies related to both the bonding as well as spin-dynamics in these compounds to much higher precision than in earlier work. These experiments were made possible by the design of a high frequency goniometer probe and a 3He temperature facility. The first single crystal NMR of any Mn12-based molecule was conducted on [Mn12O12(O2CCH2Br)16(H2O)4]-4CH2Cl2 (Mn12-BrAc). Its 55Mn NMR spectrum, field dependence, angular dependence, and spin-lattice relaxation time (T1) measurements were conducted. Most importantly, data are presented that (a) confirm the alteration of the magnetic core of these molecules when the samples are crushed into powder (a practice used in earlier studies), (b) show the presence of transverse hyperfine fields at the nuclear site, and (c) do not yield any evidence of temperature independent relaxation below 1 K, suggesting that QTM is not the dominant relaxation mechanism at these temperatures, in contrast to earlier studies. Data from single crystals of Mn12-Ac, the most studied SMM, concur with previous x-ray findings in that isomers are present. Such detailed information was not obtainable with powder samples. T1-1 measurements over 400 mK – 1 K indicate the existence of an energy barrier, in this case ~1.65 K, which does not fit the current understanding of the electronic energy diagram. This value supports an earlier, yet unexplained observation of such a level by inelastic neutron scattering. [Mn12O12(O2CCH2But)16(MeOH)4]-MeOH (Mn12-t-Bu), arguably the most interesting SMM in terms of the structure of the NMR peaks, does appear to be a much cleaner sample than Mn12-Ac. Fine structure is noticed, however, in the Mn4+ peak, requiring either the addition of a quadrupole interaction or isomers to explain the splitting. The five resonances that make up the lower frequency Mn3+ group increase in width upon moving to higher frequency, a most unusual result which may also be explained by the presence of isomers. Finally, the bulky ligands contribute to this SMM having the longest relaxation time at low temperature, with no evidence for temperature independence down to 400 mK. Again, evidence was found for a barrier of 1 K. We thus arrive at three major conclusions important to the understanding of SMM systems: 1) Single crystals provide an order-of-magnitude higher spectral resolution than oriented powder samples, but also show that the powdered samples do not represent a statistical average of a crystal, 2) transverse hyperfine fields are present at the Mn4+ site, contradicting early models which predicted an isotropic hyperfine field, and 3) 55Mn spin-lattice times shows no evidence of temperature independent behavior for any of the molecules studied, in contrast to earlier experiments on powdered Mn12-Ac. This observation could be the most important one, as it may result in a reconsideration of the effective spin Hamiltonian for the electronic system if terms must be added to account for an energy level in between the ms = ±10 and ms = ±9 states, at about 1 – 2 K above the ground state
Identifier: FSU_migr_etd-4224 (IID)
Submitted Note: A Dissertation submitted to the Department of Chemistry and Biochemistry in partial fulfillment of the requirements for the degree of Doctor of Philosophy.
Degree Awarded: Fall Semester, 2006.
Date of Defense: October 18, 2006.
Keywords: Low Temperature, T2, T1, Spin-lattice Relaxation, Mn12, SMMs, SMM, Condensed Matter
Bibliography Note: Includes bibliographical references.
Advisory Committee: Naresh Dalal, Professor Directing Dissertation; James Brooks, Outside Committee Member; Alan Marshall, Committee Member; Arneil Reyes, Committee Member; Oliver Steinbock, Committee Member.
Subject(s): Chemistry
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Host Institution: FSU

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Harter, A. (2006). ⁵⁵Mn NMR and Relaxation in Single Crystals of Mn₁₂-Ac and Analogs. Retrieved from