A series of bis [e] and [a] fused dibenzannulenes/cyclophanes have been
synthesized for the first time using benzyne-like intermediates (annulynes). These include
the dibenzannulene trans-2,9-di-t-butyl-14c, 14d-dihydro-14c-14d-dimethyldibenzo[fg,op]naphthacene 82b, and the metacyclophanedienes anti-[1,2;9,10]-
dibenzo-5, 13-di-t-butyl-8,16-dimethyl[2.2]metacyclophane 82a, and anti-[1,2-b; 9,10-b]-
dinaphtho-5,13-di-t-butyl-8,16-dimethyl[2.2]metacyclophane 85a.
From these compounds several metal complexes including trans-{μ-
[( 1,2,3,4,4a, 14b-η:8a,9,10,11,12,12a-η)-12c, 12d-dihydro-12c-12d-dimethylbenzo[
rst]pentaphene]]hexacarbonyldichromium 100, have been synthesized.
Among the bis [e] fused compounds, pairs 82a/82b and 95a/95b show reversible
and repeatable photo-switching properties both in solution and in the solid state. The
pyrene forms 82b and 95b are characterized at low temperature and they thermally return
to their cyclophane forms 82a and 95a at room temperature. A polystyrene based film of
82 shows a much better bistability required for photo-switching units. These properties
make them potential candidates for optical memory units. For the similar naphtho[e] fused
compound 95a, no pyrene isomer 95b was detected upon irradiation with UV light.
Based on the NMR data, relative bond fixing abilities (RBFA) of several species
are measured. The order is:
[special characters omitted] > Benzene > Oxanorbomadiene >
lU
Norbomadiene
The reduced species, oxanorbomene and norbomene, do not induce any significant
bond localization on the [14] annulene ring. / Graduate
| Identifer | oai:union.ndltd.org:uvic.ca/oai:dspace.library.uvic.ca:1828/9755 |
| Date | 20 July 2018 |
| Creators | Chen, Yongsheng |
| Contributors | Mitchell, Reginald H. |
| Source Sets | University of Victoria |
| Language | English, English |
| Detected Language | English |
| Type | Thesis |
| Format | application/pdf |
| Rights | Available to the World Wide Web |
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