Aza-analogues of distyrylbenzene (DSB) synthesis, structures, and properties of 1,4-phenylenediamine bisimines (PDABI)

Abstract

[ACCESS RESTRICTED TO THE UNIVERSITY OF MISSOURI AT AUTHOR'S REQUEST.] The drive for electo-optically active materials was officially initiated in 1966 with the publishing, by NASA, of a 137 page report. The "Electro-optic Projection Study" outlined the advantages of optical processing over those of electronic. These include increased bandwidth, modulation response ([pi] electron response), and decreased expense. We are focused on the creation of dipole parallel-aligned crystals as potential players for use as electro-optic materials. The successful synthesis of several near-perfect and perfect parallel dipole aligned crystal with acetophenone azines marks our first contributions to this database of materials, and we look to increase that number. The design principal that guides our material designs encompasses three major themes: acceptor and donor groups that create a molecular dipole, dipole minimization through the use of a [pi]-conjugation stopper, and arene-arene T-contacts (amongst other) as intermolecular synthons. The purpose of this study is to probe the aza-analogues of distyrilbenzene, heretofore referred to as the bisimines (Ph-C=N-Ph-N=C-Ph). In chapter 1, the design principal and synthesis of the symmetric bisimines will be presented. Chapter 2 will be a theoretical, computational investigation of the conformational profile of the single imine (benzylidene aniline) and double imine (bisimine) systems. Chapter 3 is a presentation of the observed packing interactions in the crystallized bisimines. Chapter 4 is a conformation and packing study of planar azine analogues chlorobenzaldazine and bromobenzaldazine.