Electrochemical and spectroelectrochemical characterisation of cyano and trifluoromethyl substituted polypyridines and their transition metal complexes
Delf, Alexander Robert L.
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This thesis is concerned with the electrochemical and spectroelectrochemical characterisation of cyano (CN) and trifluoromethyl (CF3) substituted polypyridine ligands and their metal complexes. The ligands investigated were X-CN-py (X = 3, 4 and 5, py = pyridine), X,X´-(CN)2-bpy) (X,X´ = 3,3´, 4,4´ and 5,5´ bpy = 2,2´- bipyridine) and X,X´-(CF3)2-bpy (X,X´ = 3,3´, 4,4´ and 5,5´). The Pt(II) complexes of the X-CN-py and X,X´-(CN)2-bpy ligands were studied along with the Fe(II) complexes of the X,X´-(CN)2-bpy and X,X´-(CF3)2-bpy ligands. Electrochemical studies of the X-CN-py ligands indicated that 2-CN-py and 4-CN-py have one reversible 1e- reduction and 3-CN-py has one quasi-reversible reduction. 4-CN-py is more easily reduced than 2-CN-py. EPR experiments on [2-CN-py]1- and [4-CN-py]1- combined with DFT calculations have indicated that the semi-occupied molecular orbital (SOMO) is delocalised over the entire molecule. The complex [Pt(4-CN-py)2Cl2] undergoes two reversible 1e- reductions, attributed to the sequential reduction of the two 4-CN-py ligands. [Pt(3-CN-py)2Cl2] was found to exhibit one irreversible reduction. The electrochemistry of the X,X´-(CN)2-bpy ligands indicated that 3,3´-(CN)2-bpy and 5,5´-(CN)2-bpy have two reversible 1e- reductions while 4,4´-(CN)2-bpy has only one reversible 1e- reduction. The reductions of 5,5´-(CN)2-bpy occur at significantly less negative potentials than those in 3,3´ or 4,4´ analogue. In-situ UV/Vis/NIR and EPR experiments on the X,X´-(CN)2-bpy ligands indicate that the reduction electron is delocalised over both the CN-py rings with the SOMO being spread across the entire molecule. [Pt(3,3´-(CN)2-bpy)Cl2] and [Pt(5,5´-(CN)2-bpy)Cl2] undergo two reversible 1e- reductions, attributed to the sequential reduction of the X,X´-(CN)2-bpy ligand. 4,4´-(CF3)2-bpy and 5,5´-(CF3)2-bpy, whose X-ray crystallographically determined structures are reported, both have one reversible 1e- reduction while 3,3´-(CF3)2-bpy exhibits an irreversible reduction. Again the 5,5´ analogue is the most easily reduced. Spectroelectrochemical results indicate that the reduction electron enters a SOMO that is delocalised over both the CF3-py rings. Substitution in the 5,5´ positions is determined to be electronically most significant. Complexes of the general formula [Fe(II)(X2-bpy)3][BF4] (where X = CN or CF3 in the 4,4´ or 5,5´ positions) exhibit three reversible ligand based reduction processes and a metal based oxidation. UV/Vis/NIR and EPR studies have confirmed that the reduction electron in each case enters a molecular orbital that is predominantly based on a bpy ligand. The redox potentials of 4-CN-py and 5,5´-(CN)2-bpy are solvent dependent with 1e- reduction of 4-CN-py and the two 1e- reductions of 5,5´-(CN)2-bpy moving to less negative potentials as the acceptor number (AN) of the solvent increases. A computational model has been developed for the study of the electronic properties of substituted bipyridines using DFT methods. This model has been used to aid the analysis of the EPR and UV/Vis/NIR spectra of the X2-bpys studied.