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Synthesis and characterization of high-spin organic materials: prototypes for the polaronic ferromagnet


Murray, Michael Mark (1997) Synthesis and characterization of high-spin organic materials: prototypes for the polaronic ferromagnet. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/T6V4-G875.


The design, synthesis and magnetic characterization of thiophene-based models for the polaronic ferromagnet are described. Synthetic strategies employing Wittig and Suzuki coupling were employed to produce polymers with extended π-systems. Oxidative doping using AsF_5 or I_2 produces radical cations (polarons) that are stable at room temperature. Magnetic characterization of the doped polymers, using SQUID-based magnetometry, indicates that in several instances ferromagnetic coupling of polarons occurs along the polymer chain. An investigation of the influence of polaron stability and delocalization on the magnitude of ferromagnetic coupling is pursued. A lower limit for mild, solution phase I_2 doping is established. A comparison of the variable temperature data of various polymers reveals that deleterious antiferromagnetic interactions are relatively insensitive to spin concentration, doping protocols or spin state. Comparison of the various polymers reveals useful design principles and suggests new directions for the development of magnetic organic materials. Novel strategies for solubilizing neutral polymeric materials in polar solvents are investigated.

The incorporation of stable bipyridinium spin-containing units into a polymeric high-spin array is explored. Preliminary results suggest that substituted diquat derivatives may serve as stable spin-containing units for the polaronic ferromagnet and are amenable to electrochemical doping. Synthetic efforts to prepare high-spin polymeric materials using viologens as a spin source have been unsuccessful.

Item Type:Thesis (Dissertation (Ph.D.))
Subject Keywords:Chemistry
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Dougherty, Dennis A.
Thesis Committee:
  • Myers, Andrew G. (chair)
  • Grubbs, Robert H.
Defense Date:17 June 1996
Non-Caltech Author Email:michaelmarkmurray (AT)
Record Number:CaltechTHESIS:02202014-081804882
Persistent URL:
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:8088
Deposited By: Dan Anguka
Deposited On:20 Feb 2014 17:13
Last Modified:09 Nov 2022 19:19

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