Synthesis Furan, Phenanthrene-Containing Cyclophenes
Date Issued
2008
Date
2008
Author(s)
Bai, Hao-Tien
Abstract
Cyclophanes have provided useful models for the investigation of through-space interactions between chromophores. Heterophanes also were interesting systems, but the discussing of furan-containing cyclophene was rare. It was well documented that phenanthrene-containing cyclophene, such a ring and planar aromatic structure was easy aggregated in photophysic. Recently, we have detailed a new series of furan-containing teraryl cyclophene derivatives 40a-f and 67. And two keys to syntheses were one-pot furan annulation and the McMurry reaction. It is noteworthy that they exhibit unusually large Stokes shifts and NLO properties through EFISH or HRS experiment. In order to going deeper to these cyclophenes, we obtained furan, phenanthrene-containing cyclophenes 69 and 70 which exhibit NLO properties and μβ value. It’s different property that a double bond as an electron acceptor, when cis-stilbene of 67 was replaced to phenanthrene of 69 or 70. And 69 contained the high rigid structure and a strong twisted double bond, which were proved by dynamic NMR experiment and DFT calculation. Such a twisted system may thus induce significant enhancement in hyperpolarizability. It’s interesting to note that 70, contained the strong electron withdrawing group (-CO2Et), was different property that charge transfer could only occur in the furan moiety with ester group from others. We expected a bridged double bond as an electron acceptor and furan as an electron donor for optical nonlinearity of cyclophenes may only take place in n-Bu substituted cases (40a, 67 and 69).
Subjects
Furan
Phenanthrene
Cyclophenes
NLO
Type
thesis
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