Warrick K. C. Lo

Synthesis, Characterization, and Photocatalytic H2-Evolving Activity of a Family of [Co(N4Py)(X)]n+ Complexes in Aqueous Solution

A series of [Co(III)(N4Py)(X)](ClO4)n (X = Cl(-), Br(-), OH(-), N3(-), NCS(-)-κN, n = 2: X = OH2, NCMe, DMSO-κO, n = 3) complexes containing the tetrapyridyl N5 ligand N4Py (N4Py = 1,1-di(pyridin-2-yl)-N,N-bis(pyridin-2-ylmethyl)methanamine) has been prepared and fully characterized by infrared (IR), UV-visible, and NMR spectroscopies, high-resolution electrospray ionization mass spectrometry (HRESI-MS), elemental analysis, X-ray crystallography, and electrochemistry. The reduced Co(II) and Co(I) species of these complexes have been also generated by bulk electrolyses in MeCN and characterized by UV-visible and EPR spectroscopies. All tested complexes are catalysts for the photocatalytic production of H2 from water at pH 4.0 in the presence of ascorbic acid/ascorbate, using [Ru(bpy)3](2+) as a photosensitizer, and all display similar H2-evolving activities. Detailed mechanistic studies show that while the complexes retain the monodentate X ligand upon electrochemical reduction to Co(II) species in MeCN solution, in aqueous solution, upon reduction by ascorbate (photocatalytic conditions), [Co(II)(N4Py)(HA)](+) is formed in all cases and is the precursor to the Co(I) species which presumably reacts with a proton. These results are in accordance with the fact that the H2-evolving activity does not depend on the chemical nature of the monodentate ligand and differ from those previously reported for similar complexes. The catalytic activity of this series of complexes in terms of turnover number versus catalyst (TONCat) was also found to be dependent on the catalyst concentration, with the highest value of 230 TONCat at 5 × 10(-6) M. As revealed by nanosecond transient absorption spectroscopy measurements, the first electron-transfer steps of the photocatalytic mechanism involve a reductive quenching of the excited state of [Ru(bpy)3](2+) by ascorbate followed by an electron transfer from [Ru(II)(bpy)2(bpy(•-))](+) to the [Co(II)(N4Py)(HA)](+) catalyst. The reduced catalyst then enters into the H2-evolution cycle.

Antimicrobial Properties of Mono- and Di-fac-rhenium Tricarbonyl 2-Pyridyl-1,2,3-triazole Complexes

A family of mono- and di-fac-rhenium tricarbonyl 2-pyridyl-1,2,3-triazole complexes with different aliphatic and aromatic substituents was synthesized in good-to-excellent yields (46–99 %). The complexes were characterized by 1H and 13C NMR spectroscopy, infrared spectroscopy, electronic (UV-visible) spectroscopy, high-resolution electrospray mass spectrometry, and elemental analyses. In four examples, the solid-state structures of the rhenium(i) complexes were confirmed by X-ray crystallography. The family of the mono- and di-rhenium(i) complexes and the corresponding 2-pyridyl-1,2,3-triazole was tested for antimicrobial activity in vitro against both Gram-positive (Staphylococcus aureus) and Gram-negative (Escherichia coli) microorganisms. Agar-based disk diffusion assays indicated that most of the rhenium(i) complexes were active against Staphylococcus aureus and that the cationic rhenium(i) complexes were more active than the related neutral systems. However, in all cases, the minimum inhibitory concentrations for all the complexes were modest (i.e. 16–1024 µg mL–1).

A Dinuclear Platinum(II) N4Py Complex: An Unexpected Coordination Mode For N4Py

The polypyridyl compound N,N-bis(2-pyridylmethyl)-N-bis(2-pyridyl)methylamine (N4Py) acts as a bridging ligand and coordinates to two Pt(II) ions giving an unexpected diplatinum(II) complex, whose photophysical and anticancer properties were investigated.