Title

The synthesis and structure of novel carborane based and related nonlinear optical materials

Date of Award

2003

Degree Type

Dissertation

Degree Name

Doctor of Philosophy (PhD)

Department

Chemistry

Advisor(s)

James T. Spencer

Keywords

Carborane, Nonlinear optics, Hydrindacene, Iodoethynylferrocene

Subject Categories

Chemistry | Physical Sciences and Mathematics

Abstract

This work describes the synthesis and characterization of new and unique precursor compounds to nonlinear optical molecular species. Chapter 1 provides a brief introduction to nonlinear optics and also presents some calculations to demonstrate how carborane molecules substituted with charged donor and acceptor species would have exceptionally high β values.

Chapter 2 details the syntheses of various cycloheptatriene- and/or cyclopentadiene-substituted meta -carborane cage compounds. Described is the synthesis and structure of closo -1,7-[1-(1-C 7 H 6 )-7-(2,5-(CH 3 ) 2 -3,4-(C 6 H 5 ) 2 CSH)C 2 B 10 H 10 ] 2 [SnCl 6 ], 32a , as confirmed by spectroscopy and X-ray crystallography. The solid state crystal structure of [(C 6 H 5 ) 3 C][SnCl 5 ]·CH 3 CN, 34 , was also determined and is presented as a comparison to help understand the crystal structure of compound 32a .

Reactions to stabilize the C 5 and C 7 rings attached to the carborane cage by the complexation of metal fragments are described in Chapter 3. The reaction of iodoethynylferrocene with a deprotonated carborane cage, [C 2 B 10 H 11 ] - , produced the compound closo -1,7-[7-(C≡C-{(η 5 -C 5 H 4 )-Fe-(η 5 -C 5 H 5 )})C 2 B 10 H 11 ], 42 . The complete spectroscopic characterization and the X-ray crystal structure are reported for this compound.

The syntheses of nonlinear optical molecular derivatives of the organic compound 1,1,3,3,5,5,7,7-octamethylhydrindacene, 48 , are described in Chapter 4. These reactions involved the bromination of 48 and then the subsequent reaction to attach either the cycloheptatriene or cyclopentadiene rings to the hydrindacene framework.

Chapter 5 provides a brief summary of the work presented here and offers additional detailed explanations concerning some of the reactions described in the previous chapters. Suggestions for potential directions of future work, based on the reactions described here, are offered.

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