Summary:
This work was conducted within the PhD thesis in the field of Inorganic
Chemistry and Inorganic Technology, at the Inorganic Laboratory of the
Chemistry Department of UoA. It covers literature photocatalytic systems for
hydrogen production with homogeneous photocatalysis, whereasexperimental deals
with the synthesis and characterization of complexes that show strong
absorptions in the visible region and could act as chromophores or
photocatalysts for hydrogen production. During this thesis complexes [Cu(4,4΄-
dcbpy)2]Cl, where dcbpy=2,2'-bypiridine-4,4'-dicarboxylate and [Cu(5,5΄-
dcbpy)2]Cl, where dcbpy=2,2'-bypiridine-5,5'-dicarboxylate, which can be used
as proton reductive catalysts, have been synthesized. Also, rhenium complexes
have been prepared following the literature procedures: [Rebpy(CO)3Br],
[Rebpy(CO)3Cl], [Rebpy(CO)3(MeCN)](PF6), [Rebpy(CO)3(NCS)](PF6), which can be
used as chromophores. All these complexes were characterized by physicochemical
methods, FT-IR, UV-Vis, 1H-NMR, cyclic voltammetry (CV), and spectroscopy
methods, emission. During this thesis the photocatalytic systems have been
tested for hydrogen production where the complexes [Rebpy(CO)3Br],
[Rebpy(CO)3Cl], [Rebpy(CO)3(MeCN)](PF6), [Rebpy(CO)3(NCS)](PF6), [Ru(bpy)3]Cl2,
[Ru(dcbpy)2Cl2], [Ru(dcbpy)2qdt] were used as photosensitizers (PS), the
complexes [Ni{S2C2(Ph)2}2], [Ni{S2C2(Ph)2}2](NEt4), [Ni{S2C2(Ph)(Ph-OCH3-4)}2],
[Ni{S2C2(Ph)(Ph-OCH3-4)}2](NEt4), [Ni{S2C2(Ph-OCH3-4)2}2],
[Ni{S2C2(Ph-OCH3-4)2}2](NEt4), [Ni{S2C2(Ph)2}2C3],
[Ni{S2C2(Ph)(Ph-OCH3-4)}2C3], [Ni{S2C2(Ph-OCH3-4)2}2C3], [Ni(bdt)2](TBA),
[Ni(bdt)2C3], [Ni(S4C3)Fe(CO)Cp*](BF4), [W{S2C2(C6H5)2}3],
[W{S2C2(C6H5)2}3](TBA), [Cu(4,4΄-dcbpy)2]Cl, and [Cu(5,5΄-dcbpy)2]Cl as proton
reductive catalysts, and the species triethanolamine TEOA and ascorbic
acid/sodium ascorbate as sacrificial electron donors. Τhe solvents used were
DMF, DMF/ H2O, CH3CN/H2O, acetone, CH2Cl2, H2O. For the detection of H2 a gas
chromatographer with a thermal conductivity detector (TCD) was used.
