The Influence of Auxiliary Ligands on the Photophysical Characteristics of a Series of Ruthenium (II) Polypyridyl Complexes

A series of ruthenium polypyridyl complexes were studied using UV/Vis absorption and luminescence spectroscopy as well as luminescence lifetime determination by time correlated single photon counting (TCSPC). The complexes were characterised with regard to the variation in the electronic band-gap as a result of the sequential variation of the auxiliary ligand 2,2’-bipyridine (bpy), 1,10-phenanthroline (phen) and 2,2’-biquinoline (biq) ligands while the main ligand remained constant for three different main ligand types. Luminescence yields were calculated and correlated with structural and electronic variation. It was found that both the absorption and emission characteristics could be tailored through the systematic variation of the electron affinity of the individual auxiliary ligand. This was shown to be the case regardless of the functional group at the end of the main ligand. Stokes shift and Raman spectroscopy was employed as a means to gauge the effect of ligand change on the conjugation and vibrational characteristics of the complexes. Luminescence yield and lifetimes were also shown to be well-defined with regards to systematic structure variations. The well-defined trends established elucidate the effect which variation of auxiliary ligands has on the electronic characteristics of the ruthenium polypyridyl systems. These well-defined relationships can potentially be extended to optimise luminescence yield and lifetimes and therefore suitability of such compounds for the application in for example photodynamic therapy

Synthesis, characterisation and DNA intercalation studies of regioisomers of ruthenium (II) polypyridyl complexes

Regioisomers of the functional group of the main ligand (L) on a series of [Ru(phen)2L]2+and [Ru(bpy)2L]2+ complexes, where phen is 1,10 phenanthroline and bpy is 2,2′-bipyridine, were synthesised to investigate the interaction with deoxyribonucleic acid (DNA) as potential therapeutics. UV–Vis binding titrations, thermal denaturation and circular dichroism were used to evaluate their interaction with DNA. The conclusions indicated the significance of the auxiliary ligand; especially 1,10-phenanthroline has on the binding constants (Kb). The systematic variation of auxiliary ligand(phen or bpy), and polypyridyl ligand (4-(1H-Imidazo[4,5-f][1,10]phenanthrolin-2-yl)benzonitrile (CPIP), 2-(4-formylphenyl)imidazo[4,5-f] [1,10] phenanthroline (FPIP), 2-(4-bromophenyl)imidazo[4,5-f][1,10]phenanthroline (BPIP) and 2-(4-nitrophenyl)imidazo[4,5-f] [1,10] phenanthroline (NPIP), split in terms of functional group change were investigated for DNA interaction. The CPIP analogues in particular were investigated for the regioisomerism (ortho, meta, para) effect of the nitrile group on the ligand. It was found that both the DNA interaction could be tailored through the systematic variation of the electronic nature of the individual auxiliary ligand and to a lesser extent the functional group and regioisomeric change. Preliminary cell line studies have been carried out to determine the selectivity of the complexes against cell lines such as A375 (Skin Cancer), HeLa (Cervical Cancer), A549 (Lung Cancer), Beas2B (Lung Normal Cell) and MCF-7 (Breast Cancer). Complexes which had strong DNA interactions in the binding studies have proven to be the most efficacious against certain cell lines. Establishing well-defined structure property relationships when looking at trends in spectroscopic properties and DNA binding will aid in the intelligent design of potential therapeutic complexes

Structure-Property Relationships for a Series of Ruthenium(II) Polypyridyl Complexes Elucidated through Raman Spectroscopy

A series of ruthenium polypyridyl complexes were studied using Raman spectroscopy supported by UV/Vis absorption, luminescence spectroscopy, and luminescence lifetime determination by time-correlated single photon counting (TCSPC). The complexes were characterised to determine the influence of the variation of the conjugation across the main polypyridyl ligand. The systematic and sequential variation of the main polypyridyl ligand, 2-(4-formylphenyl)imidazo[4,5-f][1,10]phenanthroline (FPIP), 2-(4-cyanophenyl)imidazo[4,5-f][1,10]phenanthroline (CPIP), 2-(4-bromophenyl)imidazo[4,5-f][1,10]phenanthroline (BPIP), and 2-(4-nitrophenyl)imidazo[4,5-f][1,10]phenanthroline (NPIP) ligands, allowed the monitoring of very small changes in the ligands electronic nature. Complexes containing a systematic variation of the position (para, meta, and ortho) of the nitrile terminal group on the ligand (the para being 2-(4-cyanophenyl)imidazo[4,5-f][1,10]phenanthroline (p-CPIP), the meta 2-(3-cyanophenyl)imidazo[4,5-f][1,10]phenanthroline (m-CPIP) and 2-(2-cyanophenyl)imidazo[4,5-f][1,10]phenanthroline (o-CPIP)) were also characterised. Absorption, emission characteristics, and luminescence yields were calculated and correlated with structural variation. It was found that both the electronic changes in the aforementioned ligands showed very small spectral changes with an accompanying complex relationship when examined with traditional electronic methods. Stokes shift and Raman spectroscopy were then employed as a means to directly gauge the effect of polypyridyl ligand change on the conjugation and vibrational characteristics of the complexes. Vibrational coherence as measured as a function of the shifted frequency of the imizodale bridge was shown to accurately describe the electronic coherence and hence vibrational cooperation from the ruthenium centre to the main polypyridyl ligand. The well-defined trends established and elucidated though Raman spectroscopy show that the variation of the polypyridyl ligand can be monitored and tailored. This allows for a greater understanding of the electronic and excited state characteristics of the ruthenium systems when traditional electronic spectroscopy lacks the sensitivity

Synthesis and Spectroscopic Analysis of Therapeutic Ru(II) Complexes

The aim of this study is to synthesise and characterise new ligands based on a 1,10-Phenanthroline-5,6-dione backbone and their respective Ru(II) complexes; Ru(bpy)2mfmp, Ru(bpy)2fmp and Ru(bpy)2NO2-mp as shown in figure 1.The synthesis of the ligands will be discussed and a variety of Ru(II) complexes. A brief insight of the electronic and NMR spectroscopy will be presented along with preliminary photochemical results such as extinction coefficients, quantum yields and luminescence lifetimes. Ruthenium complexes have well established synthetic and photochemical properties.1The objective of this work is to synthesise Ru(II) complexes for the applications of potential therapeutics. In order to establish their uses in medicinal applications we must first ensure their purity and photochemical properties

Spectroscopic Analysis of Therapeutic Drugs.

The aim of this project was to investigate the photochemistry of three new Ruthenium (II) complexes as possible therapeutics and their associated ligands. The objectives were to use the following spectroscopic techniques: Absorption, Emission and Raman spectroscopy. Luminescent lifetime measurements were obtained by laser studies (Nd:YAG laser and Time coupled single photon counting (TCSPC) )

Metal Drugs for Multimodal Applications

This paper outlines the roll-out of a project called SwitchOnSTEM.ie that aims to enhance Irish Higher Education (HE) STEM engagement with second level pupils. Through providing freely available all-inone resources for hands-on activities that can be used by HE staff and students at STEM events, it aims to remove barriers to participation in STEM engagement. The project was funded by Science Foundation Ireland’s SFI-Discover programme in 2015. An interdisciplinary STEM team from five Higher