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Title:Effect of Pressure on Intramolecular Charge-Transfer and Spin-Crossover Materials
Author(s):Hammack, William Scott
Doctoral Committee Chair(s):Drickamer, Harry G.,
Department / Program:Chemical Engineering
Discipline:Chemical Engineering
Degree Granting Institution:University of Illinois at Urbana-Champaign
Degree:Ph.D.
Genre:Dissertation
Subject(s):Engineering, Chemical
Abstract:In this work we consider two classes of materials, namely (1) materials that exhibit an intramolecular electron transfer (IET) and (2) materials that can exist in either a high- or a low-spin electronic configuration. These materials are studied as crystalline solids, doped into polymers, and in solution. In general there are two aspects we consider: (1) in what way does pressure affect the electronic structure of these two classes of materials and (2) what is the relationship between bulk and local (or molecular) properties in these types of materials. The IET materials studied take a variety of forms: between two transition metal moieties (a mixed-valence molecular), in an organic charge-transfer complex, and in an inorganic-organic donor-acceptor complex.
The major results are (1) that with pressure, the high-spin complex (Fe(6-Me-py)$\sb3$tren) (ClO$\sb4$)$\sb2$ will convert to a low-spin electronic ground state in acetone and dichloromethane solutions in a pressure range of 10.0 kbar; (2) with pressure we can control the degree of electronic coupling and the energy required to photo-induce an electron transfer in the (Cl$\sb5\cdot$5H$\sb2$O) salt of the Creutz-Taube mixed valence ion and in the (Fe(CN)$\sb6$) $\sp{4-}\cdot$DMV$\sp{2+}$ ion pair; (3) the peak maxima of the charge-transfer bands of a series of pyridinium-N-phenoxide betaine dyes in alcoholic and polymeric solvents correlate well with the quantity (D$\sb{\rm s}$ $-$ 1)/(D$\sb{\rm s}$ + 2), where D$\sb{\rm s}$ is the static dielectric constant of the solvents; and (4) the position of the intervalence electronic absorption band of a binuclear mixed-valence ion in solution does not correlate with the quantity (1/n$\sp2$ $-$ 1/D$\sb{\rm s}$) as predicted by the Marcus continuum model for the solvent reorganizational energy. Results (1) and (2) above are examples of the use of pressure to change the electronic structure of a material, while results (3) and (4) show how pressure can be used to vary the bulk properties of a material, either continuously or discontinuously, and thereby determine the relationship between the bulk and local properties of a material.
Issue Date:1988
Type:Text
Description:111 p.
Thesis (Ph.D.)--University of Illinois at Urbana-Champaign, 1988.
URI:http://hdl.handle.net/2142/69799
Other Identifier(s):(UMI)AAI8908698
Date Available in IDEALS:2014-12-15
Date Deposited:1988


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