<p>Obtaining a
greater understanding of photo-induced electron-transfer (PET) processes is key
to synthesizing photovoltaic materials with enhanced efficiency. Gaining knowledge about the structure
property relationship in photo-active donor-bridge-acceptor (<i>D-B-A</i>)
dyads will help to optimize electronic and photoelectronic materials. Metal
acetylide complexes have attracted increasing interest for their potential
applications as building blocks for electronic and photoelectronic materials.
Their unique υ(C≡C) (2000-2100 cm<sup>-1</sup>) allows for selective
excitation, making them an appealing target for attenuating PET processes
across a metal acetylide backbone. The following topics will be discussed: i.) an overview of
M(cyclam′) alkynyl chemistry, where M = Cr, Fe, Co, or Ni, with a focus on
reactivity and spectroscopy, ii.) selective synthesis
of dissymmetric species, utilizing a Co<sup>III</sup>(cyclam) (1,4,8,11-tetraazacyclotetradecane)
alkynyl bridge, iii) synthesis and characterization of metal alkynyl <i>D-B-A</i> dyads <i>trans- </i>[R'<sub>2</sub>N-4-C<sub>6</sub>H<sub>4</sub>C<sub>2</sub>-Co<sup>III</sup>(cyclam)-C<sub>n</sub>-NAP<sup>R</sup>]<sup>+
</sup>(n = 2 or 4), where the chromophore acceptor is NAP<sup>iPr</sup> (<i>N</i>-isopropyl-1,8-napthalimide) and the
putative donor is -C<sub>6</sub>H<sub>4</sub>-4-NR'<sub>2</sub> (R' = Me or Ph-4-OMe), iv.) design
and synthesis of <i>D-B-A</i> derivatives, alter NAP<sup>R</sup> (R = mesityl,
methyl, 1-ethylpropyl, 2-ethylhexyl, or octyl) to tune reactivity and
crystallinity, v.) electronic and spectroscopic influence the bridging center
on <i>A</i>, and vi.) effect of η<sup>2</sup>
coordination of MX<sub>2</sub> (MX<sub>2</sub> = CuCl<sub>2</sub> or Ag(NO<sub>3</sub>)<sub>2</sub>)
to the alkyne bridge on electron transfer. </p>
| Identifer | oai:union.ndltd.org:purdue.edu/oai:figshare.com:article/8870831 |
| Date | 12 August 2019 |
| Creators | Susannah Dawn Cox Banziger (6954347) |
| Source Sets | Purdue University |
| Detected Language | English |
| Type | Text, Thesis |
| Rights | CC BY 4.0 |
| Relation | https://figshare.com/articles/Synthesis_and_Structural_Studies_of_Donor-Bridge-Acceptor_Complexes_Based_on_Co_III_cyclam_Acetylides/8870831 |
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