THE SYNTHESIS AND PHOTOPHYSICAL CHARACTERIZATION OF MACROCYCLIC CHROMIUM(III) COMPLEXES

Description

<p>Tetraazamacrocycles, such as cyclam (1,4,8,11-tetraazacyclotetradecane), are useful
ancillary ligands in the formation of organometallic complexes. Coordination of
a 3d metal can lead to the formation of square planar complexes, such as with
Ni^II and Cu^II, or octahedral complexes upon coordination
of additional ligands, such as with Co^II/III and Cr^II/III.
Notably with Cr, a mixture of <i>cis-</i> and <i>trans-</i>octahedral
complexes are formed, and the isomerism can be influenced through <i>C</i>-substitution
of the cyclam macrocycle. Herein, Cr^III complexes featuring <i>C</i>-substituted
cyclam derivatives and either redox-active ligands or alkynyl ligands are
reported.</p>

<p>Chapter 1 features an introduction
to the photophysical processes of Cr(III), an overview of cyclam and its
derivatives, and a brief review of Cr^III(cyclam/cyclam’) bis-alkynyl
complexes for various applications. Chapter 2 discusses the structural,
optical, electronic, and magnetic characterizations of <i>cis</i>-[Cr(HMC)catecholate]⁺
and <i>cis</i>-[Cr(HMC)semiquinonate]²⁺ complexes, which feature redox-active
catecholate and semiquinonate ligands. Chapter 3 highlights a series of <i>trans</i>-[Cr(HMC)(C₂Ar)Cl]⁺
complexes, which expands upon prior research on bis-alkynyl complexes. Chapter
4 discusses how a different <i>C</i>-substituted cyclam derivative, MPC, is
used to produce <i>trans</i>-[Cr(MPC)Cl₂]⁺ starting
material in higher quantity than the HMC derivative. This allows for higher
amounts of <i>trans</i>-[Cr(MPC)(C₂Ar)₂]⁺
complexes to be synthesized, making it a more practical macrocycle for the
future pursuit of dissymmetric bis-alkynyl complexes.</p>

Links & Downloads

1. 10.25394/pgs.15025899.v1

Tags

Inorganic Chemistry

Cyclam Derivatives

chromium(III) complexes

Additional Fields

Identifer	oai:union.ndltd.org:purdue.edu/oai:figshare.com:article/15025899
Date	21 July 2021
Creators	Ashley Jo Schuman (11161362)
Source Sets	Purdue University
Detected Language	English
Type	Text, Thesis
Rights	CC BY 4.0
Relation	https://figshare.com/articles/thesis/THE_SYNTHESIS_AND_PHOTOPHYSICAL_CHARACTERIZATION_OF_MACROCYCLIC_CHROMIUM_III_COMPLEXES/15025899