Association of enantiopure TRISPHAT anion (1) with chiral spiro [Cu(LL')2] complexes (LL' = 2-R-phen, 2, 6-R-bpy, 3, and 2-iminopyridine, 4) leads to an efficient NMR enantiodifferentiation. Variable temperature 1H NMR spectroscopy has been used to determine the isomerisation kinetics of these pseudo-tetrahedral complexes and to evaluate their configurational stability; the latter depending on ...

Alkylation reactions of α-carboxylate phosphabetaines were carried out and studied to enhance the biological activity previously synthesized carboxylate phosphabetaines. As a result these reactions, original structure was destroyed with formation quaternary salts phosphonium triiodide. The composition confirmed by complex physical research methods, including NMR, IR spectroscopy, elemental anal...

SYNTHESIS AND HETEROALLENE REACTIVITY OF BIS(ALDIMINO)PYRIDINE NICKEL COMPLEXESIN FOUR DIFFERENT OXIDATION STATESbyBLAKE R. REED August 2016Advisor: Dr. Stanislav Groysman Major: ChemistryDegree: Doctor of PhilosophyA series of redox non-innocent bis(aldimino)pyridine ligands were synthesized. Thesewere then reacted with nickel(II) salts to form Ni[NNN]X2 complex...

The new diimine ligand 3,8-di-n-pentyl-4,7-di(phenylethynyl)-1,10-phenanthroline (1) was used for the synthesis of a range of Pt(II) complexes, viz.[Pt(1)Cl2], [Pt(1)(C triple bond C-Ph)2], [Pt(1)(C triple bond C-Fc)2] and [Pt(1)(C triple bond C-p-C6H4-C triple bond C-Fc)2](Fc = ferrocenyl). Crystal structure analyses were performed for [Pt(1)Cl2] and [Pt(1)(C triple bond C-Ph)2] and revealed t...

The intense absorption in the red part of the visible range, and the presence of a lowest charge-transfer excited state, render Platinum(II) diimine catecholates potentially promising candidates for light-driven applications. Here, we test their potential as sensitisers in dye-sensitised solar cells and apply, for the first time, the sensitive method of photoacoustic calorimetry (PAC) to determ...

Gaining chemical control over the thermodynamics and kinetics of photoexcited states is paramount to an efficient sustainable utilization photoactive transition metal complexes in a plethora technologies. In contrast energies charge transfer described by spatially separated orbitals, spin-flip cannot straightforwardly be predicted as Pauli repulsion nephelauxetic effect play key roles. Guided m...

A series of iminopyridine ligated Co(II) (1a–7a) and Ni(II) (1b–7b) complexes were synthesized. The structures of complexes 3a, 4a, 5a, 7a, 5b, and 6b were determined by X-ray crystallographic analyses. Complex 3a formed a chloro-bridged dimer, whereas 4a, 5a, and 7a, having a substituent (4a, 5a: CH3; 7a: Br) at the 6-position of pyridine, producing the solid structures with a single ligand co...

A series of air-stable nickel complexes of the form L2Ni(aryl) X (L = monodentate phosphine, X = Cl, Br) and LNi(aryl)X (L = bis-phosphine) have been synthesized and are presented as a library of precatalysts suitable for a wide variety of nickel-catalyzed transformations. These complexes are easily synthesized from low-cost NiCl2·6H2O or NiBr2·3H2O and the desired ligand followed by addition o...