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Thesis (M.S.)--University of Toledo, 2009. / Typescript. "Submitted as partial fulfillments of the requirements for The Master of Science in Geology." "A thesis entitled"--at head of title. Bibliography: leaves 99-109.

As humanity moves into the future, the demand for new electronic devices increases. Flexible electronics that could be bendable, wearable, and/or biocompatible are more desired and, fortunately, closer to our grasp than ever. In order to produce these new devices, electronic materials not based on ridged, brittle crystals are needed. One candidate for these new electronics are organic electronic materials. Organic electronic materials have the potential to lead to devices that are flexible, simple to produce and that can take advantage of state-of-the-art processes like non-linear optics, spintronics and singlet fission. In order to access these exciting new devices, however, a better understanding of the type of conjugated organic molecules on which they will be based is needed. This dissertation explores the expansion of the indenofluorene project from a rotation student’s small spin off to an examination of a full class of materials. First, this document details the synthesis of donor-acceptor-donor triads using indenofluorene starting material, the dione, as the acceptor portion. What follows is an in-depth examination of the aromatic and antiaromatic properties of the class of materials we deemed diarenoantiaromatics. The computational techniques used are expanded along with the antiaromatic core of each molecule in order to evaluate the diradical character of the core expanded molecules being synthesized by my lab mates. Finally, the synthesis and characterization of a nine ring, linear dianthracenoindacene and the progress toward the thirteen ring dipentacenoindacene isomers are described. / 10000-01-01

A systematic and efficient route to [e]-annelated derivatives of 2,7-di-t- butyl-trans-10b, 10c-dimethyl-10b,10c-dihydropyrene 34 has been achieved which provides access to the benzo, naphtho, and anthro derivatives of 34, by means of a Diels - Alder reaction of an aryne with a furan. Reaction of the annulyne derived from bromide 50 with furan gave adduct 52 which could be both deoxygenated to benzo derivative 53 and reacted with tetrazine 54 to yield the annuleno furan 55 which subsequently with benzyne and 2,3-naphthalyne yielded adducts which were deoxygenated to naphtho and anthro derivatives 57 and 59. Reaction of the furan 55 with the benzoannulyne derived from 65 gave the cyclophane fused pyrene 68, while reaction of the annulyne derived from 50 with the bisfuran 62 gave the chrysene bis pyrene 60. These fused dihydropyrene derivatives are all photochromic, and the photoisomerizations were studied In each case. Dihydropyrenes 53, 57, 59, and 65 are simple photoswitches, while 60 and 68 are more complex multiple state switches. In each case the kinetics of the MOD to DMDHP reaction was followed to obtain the activation energy, enthalpy, and entropy. It was found that the activation enthalpies and energies decreased through the series, from the benzo to the naphtho to the anthro system. This suggested that the transition states for the MCD to DMDHP reactions were stabilized by resonance with the respective annelated fragments. Detailed analysis of the NMR data of all compounds yielded an experimental aromaticity scale in which δ(Me) or δ(H4) could yield information to obtain the relative resonance energy of the annelating fragment. Correlations between methyl and H4 protons were obtained and compared to related systems. / Graduate

Chlorination of 2-methyl-2-aryloxypropanoic acids with aqueous hypochlorous acid gives spiro chloro adducts in moderate to high yields. In chlorination of 2-methyl-2-(2-methylphenoxy)propanoic acids, 1,2-adducts are formed, while in the case of 2-methyl-2-(4-methylphenoxy)propanoic acids, 1,4-adducts are obtained. In addition to the spiro adducts, 2-methyl-2-(4-chlorophenoxy)propanoic acids in the former case, and 2-methyl-2-(2-chlorophenoxy)propanoic acids in the latter case are formed, respectively. No 6-chlorosubstituted products are detected on chlorination of any of the substrates. Chlorination of 2-methyl-2-(2,4-dimethylphenoxy)propanoic acid affords only the 1,4-adduct. However, chlorination of 2-methyl-2-(5-chloro-2,4-dimethylphenoxy)propanoic acid gives both the 1,2- and the 1,4-adduct. 2-Methyl-2-(3,5-di-t-butylphenoxyl)propanoic acid on chlorination yields the diastereomeric secondary chloro adduct, 8-chloro-7,9-di-t-butyl-3,3-dimethyl-1,4-dioxaspiro (4,5) deca-6,9-dien-2-one. Under neutral and non-polar conditions, most of the 1,2-adducts undergo a thermal rearrangement of the chlorine which is shown to be a (1,5) sigmatropic chlorine shift. The rearrangement rates are highly dependent on the nature of the substituents in the diene systems. Under acidic and non-nucleophilic conditions, most of the 1,4-adducts undergo an intramolecular 1,2 chlorine shift followed by aromatization to give the 3-chloro-substituted products. For the dienes in which the 3-position is originally substituted, successive 1,2 chlorine migrations and/or side chain substitution are observed. On the other hand, the 1,2-adducts under similar reaction conditions undergo an intermolecular 1,4 chlorine shift to give the 5-chlorosubstituted products. In the case that the 5-position is substituted by a methyl group, side chain substitution at the 5-methyl takes place. In the presence of added base, solvolyses of the 1,4-adducts in methanol affords simple solvolysis products and/or 1,2 carboxyl rearranged products. The kinetic studies of the solvolyses of the 1,4-adducts have been carried out. The results reveal the substituent effects on both the simple solvolysis displacement and the rearrangement reactions. / Graduate

Prior to 1965 the interactions of polycyclic aromatic hydrocarbons with DNA (Deoxyribonucleic acid) had been but moderately studied. It was concluded that, although a controversy existed, an apparent interaction occurred between DNA and certain aromatic hydrocarbon molecules and that the interaction was not an artifact of the reaction system.

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