<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>

Title: Design and synthesis of selective copper(II) chelators Author: Jan Havlík Department: Department of Inorganic Chemistry, Faculty of Science Supervisor: assoc. prof. RNDr. Jan Kotek, Ph.D. Supervisor's e-mail address: modrej@natur.cuni.cz The aim of this work was to prepare selective copper(II) chelators. Within the frame of this thesis were synthesized 13 compounds, from which 7 are new. All compounds were fully characterized by NMR spectroscopy and mass spectrometry. Copper(II) complex of synthesized ligand 1,11-bis(methylphosphinic acid)cyclam, (1,11-dipin), was studied in thermodynamic and formation/decomplexation studies. For 1,11-dipin-copper(II) complex were determined values of rate constants and activation parameters. Keywords: selective chelator, copper, cyclam derivatives, macrocyclic ligands, methylphosphonate, methylphosphinate