Dissertations / Theses on the topic 'Ruthenium-based complexes'

The research reported in this thesis was carried out in Brisbane, Australia and Calgary, Canada. The aim of the research conducted in Brisbane was to prepare a series of copper(I) and ruthenium(II) based complexes incorporating a hemilabile phosphine ligand and to determine whether or not these compounds possessed catalytic activity. The history, uses, properties and recent work incorporating hemilabile phosphine ligands is discussed in detail as well as the application of hemilabile ligands to atom transfer radical polymerization (ATRP) and the usefulness of the 'windscreen wiper' action of these ligands in polymerization. The literature synthesis and characterization of four hemilabile phosphine ligands is reported with modifications. The (2-chlorophenyl)diphenylphosphine ligand was prepared via a Grignard reaction giving a 11% yield. The (2-bromophenyl) diphenylphosphine ligand was prepared by reaction of 2-bromoiodobenzene with Ph2PSiMe3 in the presence of a palladium catalyst (MeCN)2PdCl2 which yielded 50% product. The 1-chloro-2-diphenylphosphinoethane ligand was prepared following the generation of a lithium diphenylphosphide which was added to 1,2-dichloroethane to give a 43% yield of product. The (2-benzoic-acid)diphenylphosphine ligand was prepared by hydrolysis of (2-methyl-ester-phenyl)diphenylphosphine. Following acidification of the methyl ester phosphine with HCl, the desired product was isolated in 88% yield. The synthesis and characterization of a series of copper(I) based complexes incorporating the prepared phosphine ligands involved reaction in CH3CN of the appropriate ligand with copper halides as starting material. Solution state 31P NMR and mass spectrometry were used to study many of these complexes in the solution state, whilst microanalysis, 31P CP MAS NMR and single crystal X-ray diffraction studies were used to study their solid state properties. The complexes of the type bis(2-halophenyl)diphenylphosphine copper halide were found to be three coordinate with non-chelating ligands and to be isostructural with the previously studied bis(2-methylphenyl)diphenylphosphine copper halide complexes. The synthesis and characterization of ruthenium(II) based complexes incorporating hemilabile phosphine ligands involved reaction of the appropriate ligands in MeOH with RuCl3.3H2O or RuCl2(DMSO)4 as the ruthenium source. Modes of characterization included solution state 31P NMR, mass spectrometry, microanalysis and single crystal X-ray diffraction studies. All ruthenium(II) based complexes were found to incorporate the hemilabile ligands in a chelating mode resulting in 6 coordinate structures. The preliminary polymerization testing of MMA in the presence of the copper(I) and ruthenium(II) based complexes has been reported. All complexes successfully polymerized the monomer and the resulting polyMMA showed polydispersity values ranging from moderate (3.1) to very high (6.7). Chapter 7 discusses research conducted over a 6 month period at the University of Calgary, Canada under an International Resident Fellowship award. This work involved the synthesis and characterization of scandium(III) and yttrium(III) based complexes incorporating a chelating amido-imine ligand, as potential olefin polymerization catalysts.

The research reported in this thesis was carried out in Brisbane, Australia and Calgary, Canada. The aim of the research conducted in Brisbane was to prepare a series of copper(I) and ruthenium(II) based complexes incorporating a hemilabile phosphine ligand and to determine whether or not these compounds possessed catalytic activity. The history, uses, properties and recent work incorporating hemilabile phosphine ligands is discussed in detail as well as the application of hemilabile ligands to atom transfer radical polymerization (ATRP) and the usefulness of the 'windscreen wiper' action of these ligands in polymerization. The literature synthesis and characterization of four hemilabile phosphine ligands is reported with modifications. The (2-chlorophenyl)diphenylphosphine ligand was prepared via a Grignard reaction giving a 11% yield. The (2-bromophenyl) diphenylphosphine ligand was prepared by reaction of 2-bromoiodobenzene with Ph2PSiMe3 in the presence of a palladium catalyst (MeCN)2PdCl2 which yielded 50% product. The 1-chloro-2-diphenylphosphinoethane ligand was prepared following the generation of a lithium diphenylphosphide which was added to 1,2-dichloroethane to give a 43% yield of product. The (2-benzoic-acid)diphenylphosphine ligand was prepared by hydrolysis of (2-methyl-ester-phenyl)diphenylphosphine. Following acidification of the methyl ester phosphine with HCl, the desired product was isolated in 88% yield. The synthesis and characterization of a series of copper(I) based complexes incorporating the prepared phosphine ligands involved reaction in CH3CN of the appropriate ligand with copper halides as starting material. Solution state 31P NMR and mass spectrometry were used to study many of these complexes in the solution state, whilst microanalysis, 31P CP MAS NMR and single crystal X-ray diffraction studies were used to study their solid state properties. The complexes of the type bis(2-halophenyl)diphenylphosphine copper halide were found to be three coordinate with non-chelating ligands and to be isostructural with the previously studied bis(2-methylphenyl)diphenylphosphine copper halide complexes. The synthesis and characterization of ruthenium(II) based complexes incorporating hemilabile phosphine ligands involved reaction of the appropriate ligands in MeOH with RuCl3.3H2O or RuCl2(DMSO)4 as the ruthenium source. Modes of characterization included solution state 31P NMR, mass spectrometry, microanalysis and single crystal X-ray diffraction studies. All ruthenium(II) based complexes were found to incorporate the hemilabile ligands in a chelating mode resulting in 6 coordinate structures. The preliminary polymerization testing of MMA in the presence of the copper(I) and ruthenium(II) based complexes has been reported. All complexes successfully polymerized the monomer and the resulting polyMMA showed polydispersity values ranging from moderate (3.1) to very high (6.7). Chapter 7 discusses research conducted over a 6 month period at the University of Calgary, Canada under an International Resident Fellowship award. This work involved the synthesis and characterization of scandium(III) and yttrium(III) based complexes incorporating a chelating amido-imine ligand, as potential olefin polymerization catalysts.
Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
School of Science
Faculty of Science
Full Text

Les complexes de ruthénium à ligand nitrosyle sont très connus pour posséder des propriétés photochromes qui résultent des changements de coordination du fragment Ru-NO sous irradiation à basse température. Ce phénomène comporte de nombreuses applications telles que le stockage optique de données. Ces complexes ont aussi la capacité de délivrer l'oxyde nitrique de manière photo-contrôlée. Cela présente un grand intérêt car NO est impliqué dans de très nombreuses réactions physiologiques. Cette thèse est consacrée à l'étude des facteurs qui influencent les propriétés photochromes et la photolibération de NO dans les complexes de nitrosyle de ruthénium avec des ligands pyridine ou bipyridine. Le premier chapitre de cette thèse se concentre sur une étude bibliographique approfondie. Dans le second chapitre, la synthèse et la caractérisation des complexes de nitrosyle de ruthénium avec des ligands pyridine de formule trans(X, NO)-[Ru(R-py)4XNO](PF6)2 (R-py = pyridine, 4-picoline, 3-picoline, 4-vinylpyridine, 3- carboxaldéhydepyridine et 4-chloropyridine, X= Cl, Br, I ou OH) sont étudiés. Dans le troisième chapitre, la synthèse et la caractérisation des complexes de ruthénium nitrosyle avec le ligand bipyridine de formule cis(X, NO)-[Ru(L)2XNO] Y2, (L= 2,2'-bipyridine ou 4,4'-diméthyl-2,2'-bipyridine, X= Cl, NO2 ou Br, Y= PF6 ou Br) sont discutés. Dans le quatrième chapitre, nous présentons les résultats sur l'étude de photoisomérisation des complexes présentés dans les chapitres précédents. La conversion Ru-NO/Ru-ON est estimée par spectroscopie infrarouge après irradiation par une lumière bleue à basse température à l'état solide. Le taux de population Ru-NO/Ru-ON varie entre 1 et 76%. Nous avons étudié les effets de la position cis/trans et de la nature du ligand par rapport au nitrosyle, des substituants (groupe donneur ou attracteur d'électrons) sur le ligand pyridine ou bipyridine sur la réponse photochrome. Des calculs théoriques par DFT ont permis de rendre compte des propriétés photochromes différentes entre le complexe parent avec un ligand pyridine et le ligand 4-chloropyridine. Le cinquième chapitre est consacré à l'étude de la photolibération de NO. Le rendement quantique (NO) se trouve dans la gamme 0.2-0.7. Le test de Griess a confirmé le relargage de NO
We are interested in the photoactive properties of ruthenium nitrosyl complexes. Ruthenium nitrosyl complexes are well known to possess photochromic properties which arise from the coordination changes of Ru-NO under irradiation at low temperature. This phenomenon has many applications such as high optical data storage and sensors. Ruthenium nitrosyl complexes are also very promising candidates because the photochemical delivery of bioactive small molecules such as nitric oxide (NO•) from ruthenium nitrosyl complexes presents the possibility of controlling the location, timing and dosage of NO• to physiological targets. Nitric oxide photorelease have gained wide attention after the discovery of several nitric oxide physiological functions and its involvement in different cellular processes. This thesis was devoted to studying the factors which affect the photochromic properties and NO photorelease in ruthenium nitrosyl complexes with pyridyl or bipyridyl based ligands. The first chapter of this thesis focuses on a survey of the literature related to both photoisomerization and photorelease phenomena. In chapter 2, the synthesis and characterization of ruthenium nitrosyl complexes with pyridyl based ligands with the formula trans(X,NO)-[Ru(R-py)4XNO](PF6)2, (where R-py is pyridine, 4-picoline, 3-picoline, 4-vinylpyridine, 3-carboxaldhydepyridine and 4-chloropyridine, X=Cl, Br, I or OH) are discussed. In chapter 3, the synthesis and characterization of ruthenium nitrosyl complexes with bipyridyl based ligand with formula cis(X,NO)-[Ru(L)2XNO]Y2, (L= 2,2'-bipyridine or 4,4'-dimethyl-2,2'-bipyridine, X=Cl, NO2 or Br, Y=PF6 or Br) are discussed. In chapter 4, we present the results of our investigations of nitrosyl ligand photoisomerization in Ru-NO with pyridyl and bipyridyl ligands. The conversion of Ru-NO to Ru-ON conformation was estimated by infrared spectroscopy upon irradiation by blue light at low temperature in the solid state. The values are ranged between 1-76%. We studied the effects of cis/trans ligand position to nitrosyl and the nature of substituents on pyridine or bipyridine ligand (electron donating or withdrawing group). We used theoretical calculations (DFT) to explain the different photochromic properties between parent complex with a pyridine ligand and 4-chloropyridine ligand. The fifth chapter is devoted to the study of NO photorelease. The quantum yield (NO) was estimated in the range of 0.2-0.7. Griess test was used to confirm NO delivery

Metal-organic frameworks (MOFs) have been extensively studied because of their amazing applications in gas storage, purification, photocatalysis, chemical sensing, and imaging techniques. Ruthenium polypyridyl complexes have been broadly considered as photosensitizers for the conversion of solar energy and photoelectronic materials. With this aspect, we have synthesized three new ruthenium polypyridyl based MOFs ([Ru(H2bpc)Cu(bpc)(Hbpc)2(H2O)]·5H2O (1), [Ru(H2bpc)(Fe(bpc)(Hbpc)2(H2O)2]·6H2O (2) and [Ru(H2bpc)Ni(bpc)(Hbpc)2(H2O)2]·6H2O (3)) from ruthenium(III) chloride, bpc (2,2’- bipyridine-4,4’-dicarboxylic acid) ligand, and 3d M(II) metal ions (M(II)= Cu(II), Fe(II), Ni(II)). These MOFs were synthesized under hydro or solvothermal conditions by using water, ethanol or methanol as solvents. The crystal structures of the new compounds contains zigzag chains of [Ru(bpc)3]n- complex ions linked by Cu, Fe or Ni complex ions individually. Above synthesized crystal structures were characterizing by single-crystal Xray and powder X-ray diffraction strategies, UV-vis and IR spectroscopy. Thermal properties were determining by thermogravimetric analysis. Magnetic properties were also studied.

Thesis (M. Eng.)--Massachusetts Institute of Technology, Dept. of Materials Science and Engineering, 2003.
Includes bibliographical references (leaves 39-44).
Organic light-emitting devices have the potential to create a new range of applications. They are versatile because their physical properties (color, emission efficiency) can be fine-tuned by the manipulation of their chemical structures. In this work, the novel technology of Ru(bpy)t-based devices was evaluated in the feasibility of commercializatjon. An overview was presented on current development and competing technologies within research and industry with regard to advantages and drawbacks of the technology of various organic light-emitting devices. The basic principles concerning the light emission from various devices were also presented. An intellectual property search on the technologies of the organic light-emitting devices revealed there was no patent to block the technology of organic light-emitting device based on Ru(bpy)t complex. A brief economic analysis of Ru(bpy)t-based device was proposed for targeting the display markets.
by Tsai Jang-Shiang.
M.Eng.

Includes bibliographical references.
A series of monodentate (N-) and chelating bidentate (N,N-, N,O-), monomeric and dendritic ligands based on a poly(propyleneimine) dendrimer scaffold were synthesized via Schiff base condensation reactions of the relevant amine and appropriate aldehydes. These reactions yielded air- and moisture-stable oils or solids. These ligands contained pyridyl-imine moieties and salicylaldimine moieties. These compounds were isolated in good yields and characterized using standard spectroscopic and spectrometric, analytical techniques.

Includes bibliographical references.
A series of chelating, bidentate (C,N-) monomeric and dendritic ligands based on a poly(propyleneimine) dendritic scaffold were synthesized via a Schiff-base condensation reaction of the relevant amine and either naphthaldehyde or benzaldehyde. These reactions yielded air- and moisture-stable solids or oils. These compounds were isolated in good yields and characterized using standard spectroscopic and analytical techniques.

The significant involvement of metal ions and complexes in biological processes and systems has, over recent times, led to the realization that considerable scope exists for the design of metal-based therapeutics. While considerable work in this area has been in the field of coordination complexes, the large diversity of structure and unique bonding modes of organometallic complexes also suggests that these systems may find use as therapeutic agents. This thesis seeks to explore this hypothesis through the in vitro / in vivo anticancer evaluation of a family of cationic organoruthenium Cp* arene full-sandwich complexes.
Thesis (PhD Doctorate)
Doctor of Philosophy (PhD)
School of Biomolecular and Physical Sciences
Science, Environment, Engineering and Technology
Full Text

Le transfert d'électron et d'énergie induit par la lumière dans des dispositifs moléculaires est largement étudié dans le domaine de la photosynthèse artificielle. Dans ce contexte, les dérivés du [Ru(bpy)3]2+ ont été très utilisés, en raison de leurs propriétés photophysiques favorables, à savoir des durées de vie de l’ordre des µs à température ambiante, des rendements quantiques d’émission élevés et un fort pouvoir d’oxydation et de réduction. La conception de la structure électronique des complexes de ruthénium(II) revêt une très grande importance, car celle-ci dictera les propriétés photophysiques, photochimiques et électrochimiques de ces complexes. En conséquence, le sujet principal de cette thèse est d'explorer les propriétés de coordination de nouveaux ligands tridentes sur le cation ruthénium. Ce travail décrit la synthèse de ces nouveaux ligands basés sur l'hétérocycle acridine avec différents fragments en positions 4 et 5. Les complexes de ruthénium(II) octaédriques correspondants ont ensuite été construits autour de ces ligands à base d'acridine, avec des niveaux d'énergie ajustés des états excités 3MC et 3MLCT fonctionnellement actifs. Très peu de dérivés d’acridine sont substitués aux positions 4 et 5. La stratégie de synthèse pour les ligands cibles commence sur l’acridone. La 4,5-dibromoacridine a été obtenue en quatre étapes synthétiques et ce précurseur commun a ensuite été utilisé pour la construction de ligands tridentés (NNN) avec de la pyridine et du pyrazole. De plus, un analogue de ligand tridentate (SNS) à base de thioéther acridine a été synthétisé, et un autre ligand tridentate de thioéther (SNS), sans hétérocycle acridine, a été préparé dans le but d’acquérir une certaine flexibilité dans la structure. Les complexes homoleptiques correspondants avec des métallacycles à 6 chaînons ont tous adopté une géométrie octaédrique faciale. Ainsi, les complexes hétéroleptiques ont été préparés en combinaison avec un ligand terpyridine plan afin de forcer les ligands contraints et rigides à se coordiner de manière méridienne sur le métal. Les propriétés électrochimiques, photophysiques et photochimiques de tous les complexes ont été étudiées et la structure de la plupart de ces complexes de Ru(II) a été déduite par des expériences de cristallographie par diffraction des rayons X. Les complexes bis-tridentés de Ru(II) basés sur le ligand thioéther flexible (SNS), se sont montrés photoactifs: lors d'une exposition à la lumière blanche ils subissent une réaction de photosubstitution, remplaçant le ligand thioéther tridentate par des ligands monodentates
Light-induced electron and energy transfer in molecular arrays is being extensively studied in view of artificial photosynthesis. In this context, [Ru(bpy)3]2+ derivatives have been widely used, due to their favorable photophysical properties, i.e. lifetimes in the µs range at room temperature, high emission quantum yields, and strong oxidizing and reducing capability. The electronic structural design of most ruthenium(II) complexes is of great importance by specifying the complexes’ photophysical, photochemical, and electrochemical properties. As a consequence, the main theme of this thesis is to explore the coordination properties of new tridentate ligands on the ruthenium cation. This work describes the synthesis of these new tridentate ligands based on the acridine heterocycle with different moieties at positions 4 and 5. Octahedral ruthenium(II) complexes were then constructed around these acridine-based ligands, with tuned energy levels of the functionally active 3MC and 3MLCT excited states. Very few acridine derivatives are substituted at positions 4 and 5. The synthetic strategy for the target ligands starts from acridone. The 4,5-dibromoacridine was obtained in four synthetic steps and this common precursor was subsequently used for the construction of tridentate (NNN) ligands with pyridine and pyrazole. In addition, a thioether acridine-based tridentate ligand (SNS) analogue was synthesized, and another tridentate thioether (SNS) ligand, without an acridine heterocycle, was prepared to gain some flexibility within the ligand scaffold. The corresponding homoleptic complexes with 6-membered metallacycles only adopted a facial octahedral geometry. Thus, the heteroleptic complexes were prepared in combination with a planar terpyridine ligand in order to force the constrained and rigid ligands to coordinate in a meridional fashion on the metal. The electrochemical, photophysical, and photochemical properties of all complexes were studied and the structure for most of these Ru(II) complexes was deduced by X-ray diffraction crystallography experiments. The bis-tridentate Ru(II) complexes based on the flexible (SNS) thioether ligand were photoactive: they were able to undergo a photosubstitution reaction, by replacing the tridentate thioether ligand with monodentate ligands, upon white light exposure

L’objectif de cette thèse est de préparer et caractériser de nouveaux agents théranostiques potentiels à base de complexes de ruthénium portant des molécules biologiquement actives. Pour évaluer potentiel théranostique des nouveaux composés les propriétés de luminescence et la cytotoxicité ont été considérées. Quatre nouveaux ligands portant des substituants a activité biologique: 5-(4-4’-methyl-[2,2’-bipyridine]-4-ylbut-1-yn-1-yl)pyridine-2-carbaldehyde semicarbazone (L1), 3-(5-4’-methyl-[2,2’-bipyridine]-4-ylpentyl)imidazolidine-2,4-dione (L2), 5,5-dimethyl-3-(5-4’-methyl-[2,2’-bipyridine]-4-ylpentyl)imidazolidine-2,4-dione (L3) and [1-(5-4’-methyl-[2,2’-bipyridine]-4-ylpentyl)-2,5-dioxoimidazolidin-4-yl]urea (L4) ont été prepares, caractérisés et engagés dans la synthese des complexes de ruthénium correspondants. Six complexes ont été obtenus a partir du ligand L1 ([Ru(bpy)2(L1)]2+, [Ru(Mebpy)2(L1)]2+, [Ru(tBubpy)2(L1)]2+, [Ru(Phbpy)2(L1)]2+, [Ru(dip)2(L1)]2+, [Ru(SO3dip)2(L1)]2-) et trios a partir de L2, L3 and L4 ([Ru(bpy)2(L2)]2+, [Ru(bpy)2(L3)]2+, [Ru(bpy)2(L4)]2+) (bpy = 2,2’-bipyridine, Mebpy = 4,4’-dimethyl-2,2-bipyridine, tBubpy = 4,4’-tert-butyl-2,2’-bipyridine, Phbpy = 4,4’-diphenyl-2,2-bipyridine, dip = 4,7-diphenyl-1,10-phenantroline and SO3dip = 4,7-di-(4-sulfonatophenyl)-1,10-phenantroline). Les propriétés spectroscopiques et photophysiques des composés ont été étudiées. La présence des ligands L1-L4 conduit a une décroissance du rendement quantique et de la durée de vie de l’état excité en comparaison des complexes non substitués [Ru(bpy)3]2+. Des calculs DFT montrent que les ligands L1-L4 n’influencent pas la géométrie du complexe mais accroissent le niveau énergétique de la HOMO induisant des band gap HOMO-LUMO plus faibles. Les interactions entre les complexes et l’human serum albumin (HSA) ont été étudiées. Tous les complexes préparaés montrent une tres forte affinité pour HSA – La constante d’association 105 M-1s-1 témoigne de la formation d’adduits Ru-HSA stables. Il a aussi été démontré que les complexes de ruthénium se lient préférentiellement a la poche hydrophobe des protéine, située dans le site 1 de Sudlow dans le sous domaine II A. Des études préliminaires ont montré que les complexes de ruthénium préparés presentent une activité cytotoxique vis-à-vis de diverses lignées de cellules cancéreuses. Cette activité associée aux bonnes propriétés de luminescence (rendement quantique, durée de vie) fait des nouveaux complexes des candidats potentiels pour les applications théranostiques
The main goal of this thesis was synthesis and preliminary characterization of novel ruthenium(II) polypyridyl complexes bearing biologically active molecules as potential theranostic agents. Luminescence for the diagnostic applications, and cytotoxicity for the anticancer, therapeutic applications are considered as the theranostic properties. Four new ligands containing biologically active moieties - 5-(4-4’-methyl-[2,2’-bipyridine]-4-ylbut-1-yn-1-yl)pyridine-2-carbaldehyde semicarbazone (L1), 3-(5-4’-methyl-[2,2’-bipyridine]-4-ylpentyl)imidazolidine-2,4-dione (L2), 5,5-dimethyl-3-(5-4’-methyl-[2,2’-bipyridine]-4-ylpentyl)imidazolidine-2,4-dione (L3) and [1-(5-4’-methyl-[2,2’-bipyridine]-4-ylpentyl)-2,5-dioxoimidazolidin-4-yl]urea (L4) were synthesized and characterized. The ligands were used to obtain nine novel ruthenium(II) polypyridyl complexes. Six complexes were synthesized with ligand L1 ([Ru(bpy)2(L1)]2+, [Ru(Mebpy)2(L1)]2+, [Ru(tBubpy)2(L1)]2+, [Ru(Phbpy)2(L1)]2+, [Ru(dip)2(L1)]2+, [Ru(SO3dip)2(L1)]2-) and three with ligands L2, L3 and L4 ([Ru(bpy)2(L2)]2+, [Ru(bpy)2(L3)]2+, [Ru(bpy)2(L4)]2+) (bpy = 2,2’-bipyridine, Mebpy = 4,4’-dimethyl-2,2-bipyridine, tBubpy = 4,4’-tert-butyl-2,2’-bipyridine, Phbpy = 4,4’-diphenyl-2,2-bipyridine, dip = 4,7-diphenyl-1,10-phenantroline and SO3dip = 4,7-di-(4-sulfonatophenyl)-1,10-phenantroline). The spectroscopic and photophysical properties of those complexes were determined. The presence of ligands L1-L4 in the structure of the complex decreased luminescence quantum yield and luminescence lifetime in comparison with unmodified [Ru(bpy)3]2+ complex. The theoretical calculations have shown that ligands L1-L4 do not have influence on ruthenium core geometry. However, they increased the energy of the HOMO that resulted in a shorter band gap. The simulated electronic absorption spectra were in a good agreement with the experimental data. The interactions between the studied ruthenium complexes and human serum albumin (HSA) were investigated. All studied Ru(II) complexes exhibited strong affinity to HSA with the association constant 105 M-1s-1, which suggests formation of Ru complex-HSA adducts. It was also determined that ruthenium complexes most likely bind to the hydrophobic pocket of protein, located in Sudlow’s site I in the subdomain II A. Preliminary cytotoxicity evaluation for the studied ruthenium complexes showed their cytotoxic activity towards cancer cell lines. Those results, together with good luminescence properties of the studied ruthenium complexes (luminescence lifetimes and luminescence quantum yield) make them interesting candidates for potential theranostic applications

Two series of new mononuclear ruthenium complexes with hydrophobic or hydrophilic ligands [Ru(bda)L2] and [Ru(pdc)L3] (H2bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; H2pdc = 2,6-pyridinedicarboxylic acid; L = pyridyl ligands) were synthesized and their electrochemical properties and catalytic activity toward water oxidation were examined. It was revealed that the hydrophobic ligands introduced to [Ru(bda)L2 ] improved the catalytic performance, ahnost twofold TON and TOF values were achieved compared to the [Ru(bda)] catalyst with hydrophilic ligands. The cyclic voltammogram of [Ru(bda)L2] exhibited marginal difference between the catalysts with hydrophobic ligands and hydrophilic ones, implying that the hydrophobic ligands promoted the catalytic activity by :lacilitating formation of a reaction intermediate dimer.

According to the famous axiom known as Moore’s Law the number of transistors that can be etched on a given piece of ultra-pure silicon, and therefore the computing power, will double every 18 to 24 months. However, around 2020 hardware manufacturers will have reached the physical limits of silicon. A proposed solution to this dilemma is molecular electronics. Within this field researchers are attempting to develop individual organic molecules and metal complexes that can act as molecular equivalents of electronic components such as wires, diodes, transistors and capacitors. In this work we have synthesized a number of new bi- and terdentate thiophenyl pyridine and pyridyl thienopyridine ligands and compared the electrochemical, structural and photophysical properties of their corresponding Ru(II) complexes with Ru(II) complexes of a variety of ligands based on 6-thiophen-2-yl-2,2'-bipyridine and 4-thiophen-2-yl-2,2'-bipyridine motifs. While the electrochemistry of the Ru(II) complexes were similar to that of unsubstituted [Ru(bpy)3]2+ and [Ru(tpy)2]2+, substantial differences in luminescence lifetimes were found. Our findings show that, due to steric interactions with the auxiliary bipyridyl ligands, luminescence is quenched in Ru(II) complexes that incorporate the 6-thiophen-2-yl-2,2'-bipyridine motif, while it was comparable with the luminescence of [Ru(bpy)3]2+ in the Ru(II) complexes of bidentate pyridyl thienopyridine ligands. The luminescence of the Ru(II) complexes based on the 4-thiophen-2-yl-2,2'-bipyridine motif was enhanced compared to [Ru(bpy)3]2+ which indicates that complexes of this category may be applicable for energy/electron-transfer systems. At the core of molecular electronics is the search for molecular ON/OFF switches. Based on the ability of the ligand 6-thiophen-2-yl-2,2'-bipyridine to switch reversibly between cyclometallated and non-cyclometallated modes when complexed with Ru(tpy) we have synthesized a number of complexes, among them a bis-cyclometallated switch based on the ligand 3,8-bis-(6-thiophen-2-yl-pyridin-2-yl)-[4,7]phenanthroline, and examined their electrochemical properties. Only very weak electronic coupling could be detected, suggesting only little, if any, interaction between the ruthenium cores.

Chemistry
Ph.D.
Biogenic monoamines such as dopamine play an important role as major neurotransmitters. Simultaneous determination of the concentration changes is thus crucial to understand brain function. Additionally, quantification of pharmaceutically active compounds (PhACs) and their metabolites in biological fluids is an important issue for forensic tests, clinical toxicology and pharmaceutical analysis. We have developed two postcolumn luminescence detection methods coupled to a 2-dimensional-solid phase extraction (2D-SPE) system. The postcolumn reaction methods used in this study are the redox-dependent photoluminescence-following electron-transfer (PFET) and Fenton-based chemiluminescence techniques, for the determination of certain neurotransmitter and nonsteroidal anti-inflammatory drugs (NSAIDs). A stable [Os(tmphen)3]3+ (tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline) reagent was prepared in neutral aqueous solution by oxidation of [Os(tmphen)3]2+ with lead(IV) oxide. [Os(tmphen)3]2+ and [Os(tmphen)3]3+ are characterized by absorption spectroscopy. [Os(tmphen)3]3+ stability is compared with [Ru(tmphen)3]3+ in the same pH 7 environment. The properties of Os(III) and Ru(III) complexes were investigated for use as the oxidant in a PFET system. Studies of photophysical and electrochemical properties, the stability of the Os(III) and Ru(III) complexes, and analytical application in PFET detection of oxidizable analytes are presented. The spectroscopic properties of the complexes were not very advantageous, but careful control of the detection system and reaction conditions enabled sensitive detection of the analytes. The method was fully validated and the optimized system was capable of detecting dopamine and acetaminophen at about 30.2 µg L-1 and 33.5 µg L-1, respectively. The limit of detection (LOD) was 1.5 µg L-1 for acetaminophen and 4.3 µg L-1 for dopamine. The accuracy and precision were within bioanalytical method validation limits (90.9 to 101.5 % and RSD < 12.0 %, respectively). Typical analysis time was less than 15 minutes. Two Fenton-based flow-injection chemiluminescence (CL) methods were developed and validated for the determination of naproxen. Under the optimal experimental conditions the proposed methods exhibited advantages in a larger linear range from 2,760 ng mL-1 to 207,000 ng mL-1 for the first CL method and 41.4 ng mL-1 to 700.0 ng mL-1 for the second CL method. The LOD was 13.8 ng mL-1 for naproxen. The CL mechanisms for the system, H2O2-FeIIEDTA-naproxen was further studied by batch experiments, chemiluminescence spectroscopy, fluorometry, high pressure liquid chromatography (HPLC) and Fourier transform infrared spectroscopy (FTIR). The effects of various interferences commonly found in biological and wastewater systems on the chemiluminescence intensity were also investigated. We used these methods to determine NSAIDs in commercial pharmaceutical formulations. Another application of these method was for detecting NSAIDs in biological samples. A 2x-1-Dimensional Solid Phase Extraction (2x-1D SPE) method was developed for determination of acetaminophen and naproxen in urine. This method uses both the methanol concentration and the pH advantageously to preferentially isolate analytes of interest from complex sample matrix. These methods were fully validated and had sufficient sensitivity (limit of quantification: acetaminophen; 40.41 mg L-1 - 360.0 mg L-1 and naproxen; 23.03 mg L-1 - 214.8 mg L-1) for biological matrices and applications.
Temple University--Theses

In this thesis we present the synthesis and characterization of different types of ruthenium complexes containing N-donor ligands together with dmso, Cl and H2O ligands, along with their complete characterization through spectroscopic and electrochemical techniques. The complexes have been evaluated as catalysts for olefin epoxidation and nitrile hydration in homogeneous phase. On the other hand, taking into account the importance and advantages of the heterogeneous catalysis, we have carried out the immobilization of some of these complexes on silica-type supports and we have evaluated their catalytic activity, comparing them with the analogous homogeneous systems. It is outstanding the activity of complexes with dmso and pyrazolyl ligands in nitrile hydration to the amide products using water as solvent. The heterogeneous Ru-OH2 systems have been tested in olefin epoxidation and have been reused for several runs maintaining high values of selectivity for the epoxide.
En aquesta tesi es presenta la síntesi de diferents tipus de complexos de ruteni que contenen lligands N-donadors en combinació amb lligands dmso, Cl i H2O, i la seva completa caracterització mitjançant tècniques espectroscòpiques i electroquímiques. Els complexos han estat avaluats com a catalitzadors en epoxidació d'olefines i hidròlisi de nitrils en fase homogènia. Per altra banda, tenint en compte la importància i els avantatges de la catàlisi heterogènia, s’ha dut a terme la immobilització d’alguns d’aquests complexos sobre suports tipus sílice i se n'ha avaluat l'activitat catalítica, comparant-los amb els anàlegs en fase homogènia. És destacable l'activitat dels complexos amb lligands dmso i pirazole en la hidròlisi de nitrils a amides en aigua com a dissolvent. Els sistemes Ru-OH2 heterogenis s'han avaluat en l'epoxidació d'olefines i s'han pogut reutilitzar durant diversos cicles mantenint alts valors de selectivitat per l'epòxid.

Tese de mestrado em Química Tecnológica (Química Tecnológica e Qualidade), apresentada à Universidade de Lisboa, através da Faculdade de Ciências, 2011
p-Cymene based ruthenium complexes were employed in the alkylation of tbutylamine with phenethyl alcohol by redox neutral alkylation and in the reduction of acetophenone and benzaldehyde by transfer hydrogenation. A range of in situ generated catalysts formed by [RuX2(p-cymene)]2 dimers (X=Cl or I) with dppf, DPEPhos, dippf or P(i- Bu)3 and a range of p-cymene ruthenium monomers, namely [RuCl(dppf)(p-cymene)]SbF6, [RuI(dppf)(p-cymene)]SbF6, [RuCl(dppf)(p-cymene)]BF4, [RuCl(dppf)(p-cymene)]Cl, [RuI(P(n- Bu)3)2(p-cymene)]SbF6, [RuCl(P(i-Bu)3)2(p-cymene)]SbF6, [RuCl2(P(n-Bu)3)2(p-cymene)], [RuCl(P(CH3)3)2(p-cymene)]SbF6 have been employed in these reactions. These monomers have been synthesised and characterized in this project and only [RuCl2(P(n-Bu)3)2(pcymene)] has been already reported in the literature. Results were compared in terms of conversions and the best ones for the redox neutral alkylation were with the in situ generated catalyst formed by [RuI2(p-cymene) and DPEPhos, giving 96% conversion for a catalyst/substrate ratio of 20 and with [RuI(dppf)(pcymene)] SbF6 which gave 85% conversion for a catalyst/substrate ratio of 40. These reactions have been run out in the open air without degassing or inert gas protection throughout which is not the typical approach found in the literature and that can be very appealing in the industrial point of view. The different halides incorporated in these complexes have been proved to have different effects in the catalytic activity, with iodine usually leading to more active catalysts. Some results and experiments that were performed allowed drawing some conclusions about the mechanism. For the reduction of acetophenone and benzaldehyde by transfer hydrogenation it has been demonstrated that the dimers, the dimer-phosphine pairs and the ruthenium monomers mentioned before are not the most suitable pre-catalysts for these reactions. Overall, conversions up to 73% were obtained which lag far behind the 100% reported in the literature for several other complexes. Some conclusions were drawn about the mechanism and two catalytic cycles were proposed. The brand new dimer [Ru2Cl3(DPEPhos)2(CH3CN)2]SbF6 has been serendipitously synthesised and has shown it forms catalytically active species in both the alkylation of tbutylamine and reduction of acetophenone giving moderate conversions.
Neste projecto foram sintetizados complexos de rutenio e p-cimeno que foram posteriormente avaliados do ponto de vista catalitico em reaccoes de transferencia de hidrogenio. Os complexos de rutenio e p-cimento tem demonstrado ser catalisadores/precatalisadores eficientes em varias reaccoes envolvendo compostos organicos e foi inicialmente sugerido para este projecto pela empresa biofarmaceutica Astra Zeneca o estudo da actividade catalitica do dimero [RuCl2(p-cimeno)]2 na presenca das fosfinas DPEPhos, dippf e P(i-Bu)3 em reaccoes de transferencia de hidrogenio. Esta empresa verificou que este dimero e extremamente activo na alquilacao de morfolina com álcool benzilico na presenca das fosfinas referidas (conversoes acima de 97%). No que respeita aos complexos sintetizados, levaram-se a cabo as sinteses dos dimeros de cloro e iodo de formula molecular [RuX2(p-cimeno)]2 em que X = Cl ou I e ainda de monomeros utilizando os dimeros referidos como compostos de partida. A sintese do dimero de bromo foi tambem tentada mas este revelou-se muito dificil de obter e portanto nao foi utilizado em sinteses posteriores nem nas reaccoes cataliticas. Para obter os monomeros foram ainda utilizadas fosfinas mono ou bidentadas, nomeadamente dppf, DPEPhos, dippf, P(i-Bu)3, P(n-Bu)3, P(CH3)3 ou PhPCl2 que originaram os seguintes complexos neutros ou mono cationicos: [RuCl(dppf)(p-cimeno)]SbF6, [RuI(dppf)(p-cimeno)]SbF6, [RuCl(dppf)(p-cimeno)]BF4, [RuCl(dppf)(p-cimeno)]Cl, [RuCl(P(n-Bu)3)2(p-cimeno)]SbF6, [RuI(P(n-Bu)3)2(p-cimeno)]SbF6, [RuCl(P(i-Bu)3)2(p-cimeno)]SbF6, [RuCl2P(n-Bu)3(p-cimeno)], [RuCl2P(i-Bu)3(p-cimeno)], [RuCl(P(CH3)3)2(p-cymene)]SbF6 e [RuCl2PPh(OCH3)2(p-cymene)]. Entretanto foi ainda sintetizado, por acaso, o dimero [Ru2Cl3(DPEPhos)2(CH3CN)2]SbF6 numa das tentativas de obter o monomero [RuCl(DPEPhos)(p-cymene)]SbF6. Estes compostos foram caracterizados por 1H, 13C e 31P NMR, espectrometria de massa e analise elementar. Entre eles apenas os complexos neutros [RuCl2P(n-Bu)3(p-cimeno)] e [RuCl2P(i-Bu)3(pcimeno)] ja tinham sido referenciados na literatura. As reaccoes aos quais foram submetidos os complexos sintetizados envolvem todas elas, como foi dito, transferencia de hidrogenio. Este tipo de reaccoes envolve normalmente a reducao de cetonas ou iminas e a oxidacao de alcoois ou aminas em que um catalisador transfere hidrogenio entre entre o substrato e o dador ou aceitador de hidrogenio, respectivamente. As reaccoes de transferencia de hidrogenio que aqui foram testadas foram a alquilacao da t-butilamina com alcool feniletilico designada formalmente por “redox neutral alkylation” e a reducao da acetofenona e do benzaldeido aos respectivos alcoois. O potencial catalitico dos complexos sintetizados para com as reaccoes mencionadas foi avaliado maioritariamente por 1H NMR pela percentagem de alcool de partida convertido a produto e num dos casos foi avaliado por cromatografia gasosa pela monitorizacao da concentracao de produto ao longo do tempo. Nomeadamente foi avaliado o potencial catalitico dos dimeros, dos dimeros na presenca de fosfinas e dos monomeros. Na alquilacao da t-butilamina os dimeros por si mesmo revelaram-se inapropriados uma vez que nao foram obtidas conversoes acima de 3%. Ja no caso dos dimeros na presenca de fosfinas os resultados foram significativamente melhores com o par [RuCl2(pcimeno)] 2-DPEPhos a merecer lugar de destaque uma vez que apresentou 96% de alcool de partida convertido a produto com uma proporcao substrato/catalisador de 20. Este resultado foi mesmo o melhor de entre todas as reaccoes de alquilacao levadas a cabo. Relativamente ao uso dos monomeros como pre-catalisadores, o monomero [RuI(dppf)(pcimeno)] SbF6 apresentou o resultado mais promissor com 85% de conversao com uma proporcao substrato/catalisador de 40. Estes resultados tornam-se ainda mais interessantes se levarmos em conta de que estas reaccoes foram levadas a cabo em contacto com a atmosfera, sem desarejamento ou uso de gas inerte durante a reaccao o que nao e a abordagem normalmente encontrada na literatura e que pode ser muito apelativa do ponto de vista industrial. De uma maneira geral as fosfinas bidentadas levaram a resultados promissores tanto quando usadas em combinacao com os dimeros tanto quando foram incorporadas nos respectivos monomeros. O mesmo nao pode ser dito das fosfinas monodentadas. A fosfina P(i-Bu)3 quando na presenca do dimero [RuCl2(p-cimeno)]2 levou a uma conversao de alcool a amina de apenas 28% e quando incorporada no respecivo monomero [RuCl(P(i-Bu)3)2(p-cimeno)]SbF6 nao foi alem dos 9%. Os outros complexos contendo fosfinas monodentadas e que foram testados nesta reaccao de alquilacao, nomeadamente o [RuI(P(n-Bu)3)2(p-cimeno)]SbF6, [RuCl2P(n-Bu)3(p-cimeno)], e o [RuCl(P(CH3)3)2(p-cymene)]SbF6 nao formaram qualquer especia activa cataliticamente uma vez que nao foi detectada a formacao de qualquer amina. Nesta reaccao, para alem da analise do efeito da fosfina, foi analisado o efeito do halogeneto e de uma maneira geral a presenca de iodo em vez de cloro tanto nos dimeros como nos monomeros levou a obtencao de maiores precentagens de produto e/ou reducao na quantidade de alcool por reagir. Foi ainda analisado o efeito do contra-iao, nomeadamente entre os monómeros [RuCl(dppf)(p-cimeno)]SbF6, [RuCl(dppf)(p-cimeno)]BF4 e [RuCl(dppf)(p-cimeno)]Cl e o monomero [RuCl(dppf)(p-cimeno)]Cl parece ser o melhor pre-catalisador apresentando 82% de amina obtida com uma proporcao substrato/catalisador de 20. Os resultados sugerem ainda que os complexos de formula molecular [RuX(LL)(p-cimeno)]+ onde X = halogeneto e LL = ligando bidentado sao os precursores cataliticos nas reaccoes em que sao empregues os dimeros [RuX2(p-cimeno)]2 e fosfinas bidentadas. Uma das reaccoes de alquilacao, como dito anteriormente, foi monitorizada por cromatografia gasosa. Nesta reaccao foi empregue o dimero [RuCl2(p-cimeno)]2 na presença de dppf e a monitorizacao decorreu durante 24h, isto e, o tempo a que todas as alquilações foram submetidas. No entanto esta reaccao apresentou concentracoes de produto/ conversoes muito abaixo das esperadas comparativamente a conversao obtida por 1H NMR para a mesma reaccao. Apesar disso, o padrao de reducao da concentracao de alcool e o padrao de aumento da concentracao de produto ao longo do tempo, corroboram uma das observacoes feitas acerca das conversoes obtidas por 1H NMR, nomeadamente de que durante a reaccao se esta a formar um produto secundario, nomeadamente o ester PhCH2CH2O2CCH2Ph que resulta da reaccao do aldeido formado cataliticamente com o álcool remanescente em solucao que ainda nao reagiu. No entanto, dadas as incoerências encontradas a nivel das concentracoes, da avaria do cromatografo gasoso durante um largo periodo de tempo e de algumas questoes relacionadas com o metodo, a monitorizacao por cromatografia gasosa foi abandonada. Relativamente as reducoes por transferencia de hidrogenio, nomeadamente a reducao da acetofenona e do benzaldeido estas demonstraram padroes de conversao muito semelhantes, nomeadamente os pre-catalisadores que apresentaram percentagens de conversao maiores foram os dimeros sem qualquer adicao de fosfina, ao contrario do que aconteceu nas reaccoes de alquilacao, e a presenca de iodo nos pre-catalisadores nao levou ao aumento, na grande maioria dos casos, da percentagem de produto obtido. No geral, não foram obtidas conversoes acima de 73% o que e um resultado que fica muito aquem dos 100% ja referenciados na literatura para uma larga gama de complexos. Ainda, mais uma vez, as fosfinas monodentadas parecem nao ser apropriadas para serem incorporadas nos pre-catalisadores nas reaccoes de transferencia de hidrogenio uma vez que o monómero [RuI(P(n-Bu)3)2(p-cimeno)]SbF6 nao foi alem dos 3% de acetofenona convertida ao respectivo alcool ou alem dos 12% no caso do benzaldeido. Apesar de tudo, os resultados obtidos permitiram especular um pouco acerca dos mecanismos reaccionais seguidos tendo sido propostos dois mecanismos, um para quando sao empregues apenas os dimeros e outro para quando sao empregues os dimeros na presenca de fosfinas ou empregues os monomeros. Quanto aos resultados obtidos pelo dimero [Ru2Cl3(DPEPhos)2(CH3CN)2]SbF6, este formou especies activas cataliticamente tanto nas alquilacoes como nas reducoes obtendo-se conversoes moderadas em ambos os casos, o que nao deixa de ser um resultado interessante uma vez que, tanto quanto se sabe, ainda nao foi referenciado na literatura o uso de complexos com tres pontes de cloro nas reaccoes em questao.

碩士
國立交通大學
應用化學系碩博士班
100
We design a series of benzimidazole-based heteroleptic complexs (RD series) for Dye-Sensitized Solar Cell applications. Being different with the dyes based on bipyridine-ligand we generally known, for example: N719 and Z907. The dyes we design have the advantages of simply synthesis and low costing. The power conversion efficiency of RD series dyes is comparable with N719 by large amounts of dye-loading. We knew the benzimidazole-based dye contain benzyl group had the best power conversion efficiency. Compare to N719, RD series had some defect: (1) Back reaction rate was too fast, caused the Voc was reduced. (2) The extinction coefficient was lower, against thin film device development. In our study, we design some kind of electron-acceptor or donor group, expect to reduce the back reaction rate to improve Voc value. RD12 which was design two fluoro-substituted had the best performance among this series. We used transient photocurrent/photovoltage decays measurements the thin-film samples were performed to understand the effect of fluorine atoms on cell performance. On other hand, we design thiophene group to improve the extinction coefficient. The complex contain two thiophene group (RD18) successfully increased extinction coefficient from 8000 to 17000, and it is the dye had the best power conversion efficiency among RD series. Upon optimization, the device made of the RD18 dye gives Jsc/mA cm-2 = 19.731, Voc/V = 0.758, FF = 0.704, and η= 10.58 %.

With the ever expanding utility of transition metal catalysis, there has been a thrust both to develop catalysts with unique selectivites or activites, and to understand the factors which govern these characteristics at both a fundamental and practical level. Olefin metathesis has become an essential reaction for the synthesis of small molecules in addition to polymeric materials. We have pursued two distinct ligand classes based on diaminocarbenes with novel architectures to address specific limitations within this useful class of reactions: 1) limited access to polymeric materials with controlled microstructures and 2) poor stereoselectivity in Ru-catalyzed cross-metathesis (CM) reactions. Numerous phosphines and N-heterocyclic carbenes (NHCs) have been used as ligands for Ru metathesis catalysts, and the resulting activity is very sensitive to their steric and electronic nature. We envisioned that we could take advantage of this dependence by developing a catalyst with tunable ligand donicity. Redox-switchable ligands can lead to catalysts whose selectivity and/or activity are dependent upon the ligand oxidation state. Towards this purpose, we have developed a ligand which incorporates a 1,1’-disubstituted ferrocene moiety into the backbone of a diaminocarbene (FcDAC). Upon ligation of FcDAC to various transition metals, we were able to use cyclic voltammetry and a spectroelectrochemical FT-IR experiment to show electronic communication between FcDAC and the coordinated metal. We then pursued Ru metathesis catalysts incorporating these ligands. The ring-opening metathesis polymerization of 1,5-cyclooctadiene was studied using [(FcDAC)(PPh₃)Cl₂Ru=(3-phenylindenylid-2-ene)] as the catalyst. Chemical redox reactions were used to establish the ability of FcDAC to impart redox-tunable properties to Ru metathesis catalysts. A new ligand class pioneered in our group, N-aryl,N-alkyl acyclic diaminocarbenes (ADCs), was also studied in various Ru metathesis catalysts. To our delight, these catalysts showed lower E : Z ratios than analogous NHC ligands in two representative CM reactions. We also investigated the conformational diversity of these differentially substituted ADCs given their ability to rotate about their C–N bonds, in particular, to determine how this might influence their donicity. Complexes of the type [(ADC)Ir(COD)Cl] and [(ADC)Ir(CO)₂Cl] were studied, given the wealth of structural and spectral data available for analogous compounds incorporating related ligand classes. Different conformations resulted depending on the N-substituents and the nature of the metal complex. Interestingly, the electron donating ability of ADC ligands was found to depend on their conformation, as evidenced by FT-IR and cyclic voltammetry. This established a new avenue for tuning the donor properties of differentially substituted ADC ligands. The unique properties of these novel ligand classes were demonstrated in Ru metathesis catalysts. However, on a broader level, these ligands are expected to have utility in diverse catalytic applications.
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In recent years there is an increasing awareness of the importance of chiral phosphorus ligands in transition metal organometallic chemistry because of the utility of such complexes in homogeneous catalytic reactions. This thesis deals with synthetic, spectroscopic and X-ray crystallographic studies on ruthenium complexes of chiral and achiral P-N-P type ligands, known as "diphosphazanes", with emphasis on ruthenium carbonyl clusters. Several ruthenium carbonyl clusters have been synthesized and characterized by elemental analyses, ER and NMR (lH, nC and 3lP) spectroscopic data. In several instances, the molecular structures of the clusters have been confirmed by single crystal X-ray diffraction studies. Chapter 1 provides a brief overview of various types of chiral phosphorus ligands and general synthetic routes to diphosphazanes. A brief review of the transition metal chemistry of diphosphazanes and diphosphazane chalcogenides (published since 1994) is presented A review of the literature on the carbonyl clusters of the group-8 transition metals (Fe, Ru, Os) bearing mono- and diphosphines is also included in this chapter The scope and aim of the present investigation is outlined at the end of this chapter. Chapter 2 provides the results obtained in the present investigation and a detailed discussion of the spectroscopic and crystallographic data. The essential feature of the work is summarized at the end of the chapter. Chapter 3 gives a detailed account of the experimental procedure for the synthesis of the compounds and spectroscopic and analytical measurements. The experimental details of X-ray structure determination are also given in this chapter. To save space, the coordinates of the H-atoms and the calculated and observed structure factor tables are not included. In some cases, reference to CCDC deposition number is included. The references of the literature are compiled at the end of the thesis and are indicated in the text by appropriate numbers appearing as superscripts. The compounds synthesized in the present study are represented by bold Arabic numerals and are listed in Appendix I. The abbreviations employed in the thesis conform to those generally used in Chemical Abstracts.

碩士
國立中央大學
化學學系
101
There are various types of solar cells reported and the dye-sensitized solar cells (DSSC) possessing the advantages like low-cost, simple process, multi-color, penetration, flexible, has become a key technology to developed the present solar cells. In DSSC, the photosensitizer dye used plays an important role of light absorption and helps to gain higher efficiency. In the present work we develop the complexes bearing an asymmetric structures through replacing the 2,2'-bipyridine ligand of N3 dye by the car-bene-pyridine ligand. Conjugation property of these dyes was increased through incorporation of thiophene moieties. Thus, the resulting ruthenium complexes coded as CI114, CI115 and CI117 were designed and synthesized and the dye CI115 showed better photoelectric conversion efficiency. In concern to the expensive ruthenium metal complexes based photosensitive dyes, the pure organic sensitizers showing the advantages of easy to modification of the dye structure, high absorption coefficient, low cost of synthesis and low environmental hazards, etc., were also designed. The sensitizers DD107 and DD108 representing the 2D-π-2A configuration, in which the benzene rings were incorporated in the π-bridge of the dye, were designed and synthesized. Sensitizer DD100 with D-π-A configuration was designed to evaluate the efficiency difference between 2D-π-2A and D-π-A configured sensitizers. We believe that such kind of innovative design principle will provide a new direction to the modification of organic photosensitizers to help gain higher light absorption and enhancement in overall conversion efficiency.

Thesis(M.Sc. (Chemistry)) -- University of Limpopo, 2019
Imidazolyl-ethanamine Schiff base ligands of the N^N type were prepared by condensation reaction of histamine dihydrochloride with para-substituted aldehyde derivatives to yield: (E)-N-benzylidene-2-(1H-imidazol-4-yl)ethanamine 119a, 4-((E)(2-(1H-imidazol-4-yl)ethylimino)methyl)phenol 119b, E)-N-(4-fluorobenzylidene)-2(1H-imidazol-4-yl)ethanamine 119c and (E)-N-(4-nitrobenzylidene)-2-(1H-imidazol-4yl)ethanamine 119d, which were characterised by 1H and 13C-NMR, FTIR specroscopy and HRMS. 2D-NMR experiments (1H-1H COSY and 2D-HMBC) for representative ligand 119b were performed to qualify success in the condensation reaction. An attempted reaction to coordinate Schiff base ligand 119c to zinc chloride was carried out in an NMR tube and traces of the product were observed between 12 and 24 h monitoring using 1H-NMR. Iodine promoted cyclocondensation reaction of anthranilamide and para-substituted aldehyde derivatives afforded 2-aryl-quinazolin4(3H)-ones 120a-e and subsequent chloro-aromatisation reaction in SOCl2 afforded electrophilic C4-(Cl) 2-aryl-4-chloro-quinazolines 121a-e and the compounds were characterised by 1H and 13C-NMR and FTIR spectroscopic techniques. The 2-aryl-4chloro-quinazolines served as prerequisites for de-chloro amination on the C4-(Cl) position by 2-amino-3-nitropyridine to yield 2-aryl-N-(3-nitropyridin-2-yl)quinazolin-4amine derivatives 123a-e in good yield and the derivatives were characterised by 1H and 13C-NMR, FTIR and HRMS spectroscopic techniques. The C4-(Cl) position further allowed for Sonogashira cross-coupling with ethynylpyridine to yield 2-aryl-4(ethynylpyridine)quinazoline derivatives 125a-e which were characterised by 1H and 13C-NMR, FTIR and HRMS spectroscopic techniques. The 2-aryl-4(ethynylpyridine)quinazoline served as ligands for coordination to monomeric pcymene ruthenium(ll) which yielded (ɳ6-p-cymene)RuCl2-2-aryl-4(ethynylpyridine)quinazoline derivatives 126a-e in good yield. Compounds 126a-e were characterised by 1H and 13C-NMR, FTIR and HRMS spectroscopic techniques. 2D-HMBC NMR of representative ligands 126c and 126e showed long range couplings from 1JCH to 9JCH and this was confirmed by coordination induced shifts (CIS) ranging from 1 ppm to 11 ppm. Compounds 119a-d, 123a-e and 125a-e were inductively docked into the active receptors of tyrosine kinase (PDB:2SRC), glutamine synthetase (PDB:1HTO) and oxidoreductase (PDB:3F8P). The docking scores obtained gave hits ranging from -5 to -10 Kcal/mol. Compounds 119a-d, 121a-e, 123a-e, 125a-e and 126a-e were assayed employing the broth-dilution method which gave promising anti-Mycobaterium tuberculosis activity. Compound 125e gave good activity of <0.244 µg/mL over 7 day and 14 day sampling. Coordination of ligands 125a-e to Ru(ll) group resulted in loss of activity, notably for ligand 125e.
NRF and Sasol Inzalo Bursary

碩士
國立中央大學
化學研究所
98
N-Heterocyclic carbene-pyridine-based ruthenium sensitizers derived from benzimidazolium salts provide dye-sensitized solar cells exhibiting superior performance in terms of their current densities, cell voltages and photoelectric conversion efficiencies. A solar cell sensitized with CBTR provided values of Jsc, Voc and η of 20.0 mAcm-2, 730 mV and 9.69 %, respectively, under AM 1.5 irradiation (100 mWcm-2); this performance exceeds that obtained using the traditional N719 dye (Jsc = 18.6 mAcm-2; Voc = 700 mV; η = 8.98 %).

碩士
國立彰化師範大學
化學系
105
Ruthenium compounds have great potential in the development of catalysts and anticancer drugs. A series of ketoamine ligands containing dehydroacetic acid (DHA) as the backbone has been synthesized. These ligands are the precursors for synthesizing new ruthenium complexes. Three new ruthenium compounds were synthesized by reacting the DHA-based ligands, MeC5¬H2O3-CNHRMe (L1H, R = Mes；L2H, R = NHPh) with [Ru(η6-p-cymene)Cl2]2 to form [Ru(η6-p-cymene)(MeC5¬HO3-CNMesMe)Cl] (2), [Ru(η6-p-cymene)(MeC5¬HO3-CNNHPhMe)Cl] (3), and [Ru(η6-p-cymene)(MeC5-HO4Me)Cl] (4). Compounds 2-4 were reacted with a series of sodium salt, NaX where X = N3¬¬、OCN、SCN¬¬、(CN)¬2, and six new ruthenium compounds were synthesized. These compounds are [Ru(η6-p-cymene)(MeC5¬HO3-CNMesMe)(N3)] (6), [Ru(η6-p-cymene)(MeC5HO3-CNMesMe)(NCS)] (7), [Ru(η6-p-cymene)(MeC5-HO3-CNMesMe)(NCO)] (8), {Ru(η6-p-cymene)(MeC5¬HO3-CNMesMe)[N(CN)2]} (9), [Ru(η6-p-cymene)(MeC5¬HO3-CNNHPhMe)(N3)] (11), [Ru(η6-p-cymene)(MeC5-HO3-CNNHPhMe)(NCO)] (13). All compounds have been characterized by 1H, 13C NMR spectroscopy and X-ray crystaography. The compounds 2, 3 and 4 show good reactivity in selecting hydro-carbosylation of alkynes. In addition, compound 2 has also good cancer cell inhibition activity showed PC-3 and DU145.

碩士
淡江大學
化學學系碩士班
100
A series of New type Polypyridyl-N-Heterocyclic Carbene ligands, L1(L1=6-mimbp) 、L2(L2=6-mbzimbp)、L3(L3=6-mtimbp) and their Ruthenium complexes 1(1 =[Ru(L1)2](PF6)2)、2(2 = [Ru(L2)2](PF6)2)、3(3 = [Ru(L3)2](PF6)2)、4(4 = [Ru(L1)(tpy)](PF6)2)、5(5 = [Ru(L2)(tpy)](PF6)2)、6(6 =[Ru(L3)(tpy)](PF6)2) were synthesized and characterized by NMR and Mass. Through single crystal X-ray diffraction experiments, we confirmed all this type of Ruthenium complexs exhibit distorted octahedral structure, and the Ruthenium-carbene bond lengths were shortest in all other pyridyl type NHC Ruthenium complex. The electrochemical experimental data reveal that the imidazole NHC ligand contain good σ-donation and desatblized the HOMO energy level , benzimidazole NHC ligand contain good π-acception so stabilized HOMO energy level . In electron absorption spectra of complex 1-6, two strong absorption peak in UV were assigned as π→π* transition, absorption appeared around 450 nm to 470 nm were assigned as MLCT. In electronic emission spectra，emission peak near around were assigned as 3MLCT, by measuring the quantum yield and lifetime, the experiment results indicate that the NHC ligand could expand the energy gap between 3MC and 3MLCT so increase the emission quantum yield and lifetime of 3MLCT.

Cancer is the second leading cause of death worldwide being responsible for 9.6 million deaths of a total of 18.1 million new cases in 2018. In particular, breast cancer is the most commonly diagnosed and the leading cause of death in women. Among the several types of breast cancers, the triple negative breast cancer, which is estrogen receptor negative (ER-), progesterone receptor negative (PR-) and human epidermal growth factor receptor 2 negative (HER2-) is known for its typical highly metastatic profile, with inferior prognosis and for which there is still no available effective targeted therapy. Thus, the investment in the research of new chemotherapeutic agents in this area is crucial and imperative. Within this PhD project, six new organic ligands and eighteen new ruthenium(II) cyclopentadienyl compounds were synthesized and fully characterized. These complexes were divided in three different families with the general formula [Ru(Cp)(P)(bipy)]+, where cyclopentadienyl (Cp), phosphane (P) and bipyridyl (bipy) moieties were functionalized with different groups in order to include a macromolecular ligand (polylactide - PLA and/or polyethylene glycol - PEG) and a biomolecule (biotin or curcumin) to enhance the selectivity of compounds to cancer cells, exploring both passive and active cancer targeting strategies. To assess the biological potential of the new compounds an array of in vitro studies aiming at establishing structure-activity relations was performed. The studies in hormone and nonhormone-responsive cancer cell lines encompassed the assessment of cytotoxicity, cell death, intracellular distribution (drug internalization) and anti-metastatic ability (colony formation assay) of compounds. Multidrug resistance for selected compounds on the main ABC transporters was also studied by flow cytometry. Finally, compounds’ toxicity was assessed using a zebrafish model and the lead compounds were subjected to preliminary in vivo studies using a nude mice animal model bearing triple negative breast cancer orthotopic tumors where their toxicity and efficacy on primary tumors and metastases was evaluated.
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