Title: Copper(I) complexes with phosphinonitrile donors Author: Bc. Filip Horký Department: Department of Inorganic chemistry Supervisor: prof. RNDr. Petr Štěpnička, Ph.D. Abstract: Although coordination compounds with phosphinonitrile ligands are already well known, in the vast majority of these complexes these ligands coordinate as simple P-donors with their cyano groups acting as auxiliary substituents. This led us to synthesize and study a series of Cu(I) complexes with two isomeric phosphinonitrile donors, namely 2-(diphenylphosphino)benzonitrile (Lo ) and 2-(diphenylphosphino)benzonitrile (Lp ), with different ligand-to-metal ratios and possibly characterize further coordination modes offered by these hybrid donors. This work describes the preparation of phosphinonitrile complexes from the aforementioned ligands and simple copper(I) halides (CuX, X = Cl, Br, I), pseudohalides (X = CN) and from [Cu(MeCN)4][BF4]. The products were characterized by nuclear magnetic resonance, infrared spectroscopy and elemental analysis, mass spectrometry, and their solid-state structures were determined by single-crystal X-ray crystallography. In addition, luminescent properties of the Cu(I) complexes were studied and catalytic activity of selected complexes was tested in copper-catalyzed alkyne-azide cycloaddition...

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Modern civilization highly depends on energy and finding alternative sources to fossil fuels becomes more and more necessary. The sun is the most abundant energy source available and exploiting it efficiently would result in a great environmental and economic breakthrough. Among the photovoltaic devices, dye-sensitized solar cells (DSCs) emerged for their tremendous commercial potential deriving from a combination of low-cost production and attractive features, such as flexibility and transparency, for indoor and outdoor applications. In the DSCs, a dye anchored to a semiconductor layer (typically TiO2) is responsible for capturing the sunlight and converting it into electricity. Nevertheless, many commercially available dyes for DSCs are based on a very rare metal, ruthenium, and its replacement with a cheaper, more abundant metal is desirable. A good alternative to ruthenium could be copper, which possesses similar photophysical properties in coordination with diimine ligands, but it is considerably cheaper and relatively earth-abundant. In this work, a particular “on-surface self-assembly” strategy was employed to form, on the surface of TiO2, heteroleptic copper (I) complexes with a “push-pull” design which facilitates the electron transfer from the copper (I) complex into the conduction band of TiO2 and enhances the performance of the photovoltaic devices.This thesis focuses on the investigation of the properties of five new heteroleptic copper (I) complexes bearing the same anchoring ligand but different ancillary ligands. Because of the method employed for their synthesis, a solid-state characterization of the optical and electrochemical properties on TiO2 was performed employing tools such as UV-Vis spectroscopy, cyclic voltammetry (CV), and differential pulse voltammetry (DPV). As internal benchmark through the entire characterization, the homoleptic copper (I) complex with the anchoring ligand was also studied. Some patterns between the heteroleptic complexes on TiO2 and their respective homoleptic complexes in solution were found, opening the possibility to predict the behaviour of unknown heteroleptic complexes starting from their corresponding homoleptic. Furthermore, the characterization was necessary to ensure that the complexes were fulfilling the requirements to be employed as dyes. The performances of the heteroleptic, and of the anchoring-ligand homoleptic, copper (I) complexes were then investigated as photosensitizers in DSC devices mainly by measuring the current density-voltage (J-V) characteristics at different light intensities and in the dark, the incident photon-to-current efficiency (IPCE), and electron lifetimes. As benchmark for the degree of effectiveness of the device, the state-of-the-art ruthenium (II) complex N719 was also studied. All the copper (I) complexes showed an overall similar behaviour. The J-V characteristics showed a power conversion efficiency up to 2,05% for the best performing device, which is 25% of the efficiency of DSCs based on N719. On the other hand, the least performing heteroleptic copper (I) complex studied showed an efficiency of 1,23%. From a general analysis combining all the results obtained, it may be concluded that a reason for the limited photocurrent measured through these devices can be due to incomplete dye coverage of TiO2. Despite the lower performance compared to the standard dye N719, the simplicity of the system is promising, and its considerable economic advantage could pave the way to the use of DSCs in everyday life applications. / Modernt samhälle är mycket beroende på energi och det blir allt mer akut att hitta alternativa källor till fossila bränslen. Solen är den mest riklig energikällan som finns och att utnyttja den effektivt skulle resultera i stora miljö- och ekonomiska genombrott. Färgämne sensibiliserade solceller (”dye-sensitized solar cells”; DSC) utvecklade i 90-talet för sin breda kommersiella potential som härrör från en kombination av låg kostnadsproduktion och attraktiva egenskaper, såsom möjligheter för flexibilitet och transparens. I DSC är ett färgämne förankrat till den ytan av en halvledare (vanligtvis TiO2). Färgämnet är ansvarigt för att fånga solljuset och överföra elektronerna till halvledaren för att producera el. Många kommersiella färgämnen för DSC är baserade på rutenium, en mycket sällsynt metall. Ersättning av rutenium med en billigare, rikligmetall är önskvärt mot mer hållbara DSC. En bra alternativmetall till rutenium är koppar. Komplexen av koppar(I) har liknande fotofysiska egenskaper till rutenium (II) men koppar är mer vanlig och mindre dyr än rutenium. Heteroleptiska koppar(I) komplexen med en "push-pull" design syntetiserades på ytan av TiO2 genom "ytan assisterade självmontering". "Push-pull" designen underlättar elektronöverföring från koppar(I)-komplexet till ledningsbandet av TiO2. Denna avhandling fokuseras på undersökning av egenskaperna av fem nya heteroleptiska koppar(I) komplex med den samma förankrings ligand men olika distala ligander. På grund av metoden som används i syntesen av heteroleptiska koppar(I) komplex, var karakterisering av komplexen vid optiska och elektrokemiska metoder utfördes på TiO2. Metoderna för karakterisering var UV-Vis-spektroskopi, cyklisk voltametri (CV) och differentialpuls voltametri (DPV). Som en intern standard genom hela karaktäriseringen studerades även homoleptiska koppar(I) komplex med förankringsliganden. Egenskaperna på heteroleptiska koppar(I) komplexen på TiO2 ytan kunde förutsägas från mätning av egenskaperna på homoleptiska koppar(I) komplexen. Koppar(I) komplexen är undersöktes som fotosensibiliserare i färg-sensibiliserade solceller. Effektiviteten av solcellerna med koppar(I) komplexen eller rutenium (II) komplex (N719) utvärderades genom att mäta fotokurrentdensitetsspänningen (J-V) vid olika ljusintensiteter, incidentfoton-till-ström effektiviteten (”incident photon-to-current efficiency”; IPCE) och laddningsrekombinationen (elektronlivstiden). Koppar(I) komplexen hade övergripande liknande egenskaper i solceller. En kraft omvandlingseffektivitet av 2,05% nås för den bästa solcellen med ett koppar(I) komplex. Medan den bästa effektiviteten med N719 färgämnet var 7,57%. En svaghet i självmonteringen av koppar(I) komplexen på ytan av TiO2 är den ofullständiga bindningen till ytan men självmonteringen metoden var enkel och kunde skapa många, olika färgämnen i kort tid. Trots den lägre prestandan jämfört med standardfärgen N719 är systemets enkelhet lovande, och dess stora ekonomiska fördel kan bana vägen till användningen av DSC i vardagsläget. / La civiltà moderna è fondata sull’uso dell’energia e trovare fonti alternative ai combustibili fossili è diventato sempre più necessario. La radiazione proveniente dal sole è la risorsa energetica più abbondante e disponibile sul nostro pianeta e sfruttarla al massimo comporterebbe una svolta decisiva per l’ambiente e l’economia. Tra i dispositivi fotovoltaici, le celle di Grätzel, conosciute anche come DSC dall’acronimo inglese (dye-sensitized solar cell), sono emerse per il loro enorme potenziale commerciale, dovuto alla combinazione tra basso costo di produzione e interessanti caratteristiche, come la loro flessibilità e trasparenza, che gli conferiscono la possibilità di integrazione negli edifici e l’uso in applicazioni “indoor”. Nelle DSC, un foto-sensibilizzatore, detto anche dye, ancorato ad uno strato di un materiale semiconduttore (tipicamente TiO2), è responsabile della cattura della luce solare e della sua conversione in elettricità. Tra i dye commercialmente disponibili per le DSC vi sono per lo più complessi di coordinazione basati su un metallo molto raro, il rutenio; la sua sostituzione con un metallo più abbondante ed economico è auspicabile per la diffusione di questa tecnologia. Una buona alternativa al rutenio potrebbe essere fornita dal rame, che possiede proprietà foto-fisiche molto simili al primo quando in coordinazione con diimmine; in più è abbastanza economico e relativamente abbondante sulla Terra. Una particolare strategia di "autoassemblaggio sulla superficie" è stata impiegata per formare, sullo strato di TiO2, complessi eterolettici di rame (I) con un design “push-pull” che facilita il trasferimento di elettroni dal complesso di rame (I) alla banda di conduzione di TiO2, migliorando così le prestazioni dei dispositivi fotovoltaici. Questa tesi si concentra sullo studio delle proprietà di cinque nuovi complessi eterolettici di rame (I) che possiedono lo stesso legante di ancoraggio ma diverso legante secondario. A causa del metodo impiegato per la loro sintesi, è stato necessario eseguire la caratterizzazione delle loro proprietà ottiche ed elettrochimiche direttamente sulla superficie del TiO2, utilizzando strumenti come la spettroscopia UV-Visibile, la voltammetria ciclica (CV) e la voltammetria ad impulsi differenziali (DPV). Come riferimento interno durante l'intera caratterizzazione, è stato studiato anche il complesso di rame (I) omolettico con il legante di ancoraggio. Tra i complessi eterolettici su TiO2 e i loro rispettivi complessi omolettici in soluzione, è stato individuato un trend con la possibilità di prevedere il comportamento dei primi a partire dal loro corrispondente omolettico. Inoltre, la caratterizzazione ottica ed elettrochimica è necessaria per garantire l’adeguatezza dei complessi come dye. Le prestazioni dei complessi eterolettici e del complesso omolettico con il legante di ancoraggio, sono state quindi studiate come foto-sensibilizzatori nei dispositivi DSC; in particolare è stata misurata la curva di densità di corrente – voltaggio (J-V) a diverse intensità di luce e al buio, l’efficienza quantica esterna (EQE o dall’acronimo inglese incident photon-to-current efficiency, IPCE) e infine il tempo di vita dell’elettrone nella banda di conduzione del semiconduttore. Come standard interno, per verificare l’efficacia del dispositivo, è stato anche studiato il ben noto complesso di rutenio (II), N719. Generalmente, tutti i complessi di rame (I) hanno mostrato un comportamento simile. Le curve caratteristiche J-V hanno presentato un'efficienza pari fino al 2,05% per il complesso di rame che ha dato le prestazioni migliori (25% dell'efficienza di N719). Da un'analisi generale che combina tutti i risultati ottenuti, si può concludere che una ragione per cui la foto-corrente risulta limitata potrebbe essere data dall’incompleta copertura del TiO2 da parte del complesso di rame (I) e quindi dallo scarso adsorbimento del dye. Nonostante le prestazioni inferiori rispetto allo standard N719, la semplicità del sistema è promettente e il suo notevole vantaggio economico potrebbe aprire la strada all'utilizzo delle DSC nelle applicazioni della vita quotidiana.

<p>Thin films play an important role in science and technology today. By combining different materials, properties for specific applications can be optimised. In this thesis growth of copper, copper(I) oxide and copper(I) nitride on two different substrates, amorphous SiO₂ and single crystalline α-Al₂O₃ by the so called Atomic Layer Deposition (ALD) techniques has been studied. This technique allows precise control of the growth process at monolayer level on solid substrates. Other characteristic features of ALD are that it produces films with excellent step coverage and good uniformity even as extremely thin films on complicated shaped substrates.</p><p>Alternative deposition schemes were developed for the materials of interest. It was demonstrated that use of intermediate water pulses affected the deposition pathways considerably. By adding water, the films are thought to grow via formation of an oxide over-layer instead of through a direct reaction between the precursors as in the case without water.</p><p>For growth of copper(I) nitride from Cu(hfac)₂ and ammonia no film growth occurred without adding water to the growth process. The Cu₃N films could be transformed into conducting copper films by post annealing. In copper growth from CuCl and H₂ the water affected film growth on the alumina substrates considerably more than on the fused silica substrates. The existence of surface -OH and/or -NH_x groups was often found to play an important role, according to both theoretical calculations and experimental results.</p>

Thin films play an important role in science and technology today. By combining different materials, properties for specific applications can be optimised. In this thesis growth of copper, copper(I) oxide and copper(I) nitride on two different substrates, amorphous SiO2 and single crystalline α-Al2O3 by the so called Atomic Layer Deposition (ALD) techniques has been studied. This technique allows precise control of the growth process at monolayer level on solid substrates. Other characteristic features of ALD are that it produces films with excellent step coverage and good uniformity even as extremely thin films on complicated shaped substrates. Alternative deposition schemes were developed for the materials of interest. It was demonstrated that use of intermediate water pulses affected the deposition pathways considerably. By adding water, the films are thought to grow via formation of an oxide over-layer instead of through a direct reaction between the precursors as in the case without water. For growth of copper(I) nitride from Cu(hfac)2 and ammonia no film growth occurred without adding water to the growth process. The Cu3N films could be transformed into conducting copper films by post annealing. In copper growth from CuCl and H2 the water affected film growth on the alumina substrates considerably more than on the fused silica substrates. The existence of surface -OH and/or -NHx groups was often found to play an important role, according to both theoretical calculations and experimental results.

Gold catalysis has become an important tool to achieve highly chemoselective p-acid activation. Exceptional reactivity and selectivity are often encountered under mild reaction conditions. These properties have made gold(I) complexes suitable catalysts for tremendous applications in the total synthesis of natural products. The first chapter will highlight a number of total syntheses using gold catalysis as a key step. The second chapter will cover our application of the gold(I)-catalyzed 6-endo-dig carbocyclization for the synthesis of bridgehead-substituted scaffolds and its use toward the synthesis of PPAP natural products. This research has opened our eyes to the utility of biphenylphosphine ligands, particularly JohnPhos, in gold(I)-catalysis. The reactivity and selectivity exhibited by gold(I) complexes is modulated by the nature of the ancillary ligand. Recent research rationalizes the impact of these ligands on the divergent reactivity observed between cationic and carbenoid intermediates. Our desire to favor the 6-endo-dig pathway has led us toward the discovery of another example of the diagonal reactivity that NHC carbene and biphenylphosphine ligands can bring to gold(I)-catalysis. Chapter three will explain the development of a selective gold-catalyzed synthesis of fused carbocycles . Our selective divergent synthesis of fused carbocycles, combined with the Diels–Alder reaction, has brought new synthetic opportunities. Chapter four will describe our approach toward the synthesis of various polycyclic diterpene-related frameworks. Starting with a unique linear precursor, we have developed a new “one-pot” process for the synthesis of three different polycyclic compounds related to the terpenoid family. The facile modulation of the linear precursor and the use of different dienophiles during the Diels–Alder reaction could enable the synthesis of diverse polycyclic analogues based on three principal frameworks. The gold(I)-catalyzed synthesis of fused carbocycles reached some limitations during our study. Regioselective control was found to be substantially more challenging, with terminal alkynes or alkynes bearing a sterically and electronically neutral methyl substituent. In chapter five, we will discuss how the complementarity of silver(I) catalysis to gold(I) catalysis enabled the selective divergent synthesis of three different fused carbocycles from a unique precursor. Moreover, copper(I) catalysis has given access to the 6-endo-dig pathway on terminal alkynes without the formation of a vinylidene intermediate.

La présente thèse décrit la préparation de complexes de Cu(I) stables grâce à l’ingénierie moléculaire de ligands permettant d’éviter la formation de plusieurs espèces en équilibre. Dans le cas de ligands P-N, la stratégie proposée repose sur l’utilisation d’un ligand ayant des substituants permettant de masquer un centre métallique et ainsi d’empêcher les réactions avec des nucléophiles permettant la dissociation du ligand. Dans le cas des dérivés [Cu(NN)(PP)]+, l’approche synthétique développée repose sur l’utilisation de ligands phénanthrolines macrocycliques empêchant la formation des complexes homoleptiques [Cu(NN)2]+ correspondant. Des complexes stables et luminescents ont ainsi été préparés, les rendements quantiques d’émission allant jusqu’à 46% à l’état solide pour les meilleurs luminophores. / The present PhD thesis descibes the preparation of stable Cu(I) complexes through appropriate ligand design to prevent the formation of several species in equilibrium. In the case of dinucleating P,N-ligands, the proposed strategy is based on the use of a ligand with additional substituents to shield the metal centers and thus to prevent nucleophilic attacks leading to ligand dissociation. In the case of the [Cu(NN)(PP)]+ derivatives, the proposed synthetic strategy relies on the use of macrocyclic phenanthroline ligands preventing the formation of the corresponding homoleptic complexes [Cu(NN)2]+. Stable luminescent complexes have been thus prepared, the emission quantum yields being as high as 46% in the solid state for the best emitters.

Ces travaux portent sur la conception et l’étude des propriétés photophysiques de polymères de coordination et organométalliques. Dans un premier temps, nous nous sommes intéressés aux adduits formés à partir d’halogénure de cuivre(I) (CuxXyLz ; X= I, Br, Cl). Cette famille de composés possède une grande richesse structurelle de part les conditions de synthèse (choix du ligand, stoechiométrie, choix du solvant, température…) et des propriétés de luminescence variées. Nous nous sommes concentrés sur la synthèse, la caractérisation physique et photophysique d’adduits de CuX à ligands de types monothioéther (RSR) et dithioéther (RS(CH2)nSR). Nous avons ensuite étendu notre étude aux adduits CuX coordinés à des ligands P-chirogéniques (i.e chiralité portée par l’atome de phosphore) puis à des adduits CuX coordinés à la fois par des ligands phosphorés (PPh3 ou dppm) et par des ligands mono- ou dithioéthers. Dans un second temps, nous avons voulu connaître l’impact de l’incorporation de ligands P-chirogéniques (P(C17H35)(Ph)(i-Pr)) sur les propriétés photophysiques de polymères organométalliques conjugués 1D à base de platine(II) et de ligands arylbiséthynyles (-C≡C(Ar)C≡C-). Ce type de polymère basé sur le platine(II) est souvent utilisé comme modèle dans la compréhension des transferts d’énergie dans les états excités. Ces polymères, une fois caractérisés, ont été comparés aux analogues achiraux contenant le fragment trans-Pt(P(PBu)3)2 et plusieurs différences ont été notées. Les observations et conclusions sur la relation structure-propriété sont utiles pour la conception future de matériaux photoniques portant des groupements chiraux. / This work focuses on the design and study of photophysical properties of coordination and organometallics polymers. Initially, we focused on adducts formed from copper(I) halides (CuxXyLz; X = I, Br, Cl). Indeed, these compounds have great structural diversity depending on the synthesis conditions (nature of ligand, stoichiometry, choice of solvent, temperature...) and various luminescence properties. We focused on the synthesis, physical and photophysical characterization of copper(I) halide adducts based on monothioether (RSR) and dithioether (RS(CH2)nSR) ligands. Then, we extended our study to the adducts of copper(I) halide coordinated by phosphorus P-chirogenics ligands (ie chirality carried by the phosphorus atom) and then to CuX adducts coordinated by both phosphorus ligands (PPh3 or dppm)) and mono- or dithioether ligands. Secondly, the impact of the incorporation of P-chirogenics ligands (P(C17H35)(Ph)(i-Pr)) on the photophysical properties of organometallic conjugated polymers 1D based on platinum(II) and arylbisethynyles ligands (-C≡C(Ar)C≡C-) was investigated. This type of polymer based on platinum(II) is often used as a model for the understanding of excited states energy transfers. These polymers, once characterized, were compared to the achiral analogues containing the fragment of trans-Pt(P(PBu)3)2 and several differences were noted. The findings and conclusions on the structure-property relationship are useful in the future design of photonic materials bearing chiral groups.

Dans cette thèse nous proposons une étude théorique de réactions de transmétallation entre des complexes de cuivre (I) et ceux de trois métaux du groupe principal: Si, Zn et Li. La détermination des chemins réactionnels de ces processus d'échange a été réalisée en utilisant plusieurs approches. Quand le ligand transféré est une chaîne alcoolate, ces structures sont facilement obtenues en utilisant les méthodes classiques de recherche de minima et d'état de transition, soit l'intuition chimique comme seul guide. En revanche, cette tâche devient d'une grande difficulté quand le ligand transféré est une chaîne alkyl, comme cela été le cas pour le transfert du ligand méthyle entre zinc et cuivre. Pour aborder ce problème, nous nous sommes tournés vers l'algorithme de recherche des minima GSAM, basé sur l'échantillonnage des différentes structures topologiques à partir de fragments moléculaires. Cette méthode qui a été appliquée avec succès sur des cluster atomiques ou l'hydratation de molécules biologiques, a nécessité des adaptations pour l'étude sur des espèces organométalliqes. Une fois cela réalisé, elle a démontré son efficacité dans l'étude de réactions d'intérêt expérimental. Une autre problématique abordée est la détermination du mécanisme de transfert de ligand dans un complexe bimétallique possédant un cation métallique peu coordinant (Li) et un autre très coordinant (Cu). Le réarrangement électronique associé à la transmétallation est déterminé grâce à une astuce qui consiste à remplacer Li par un atome bien coordinant tel que l'hydrogène. Cette méthode a été appliquée à l'étude du mécanisme de l'inversion de configuration dans un allénylcuprate lithié. / In this thesis we propose a theoritical study for transmetallation reactions between copper (I) complexes and those of three metals of the main group: Si, Zn and Li. Determination of reaction pathways of the exchange process was conducted in using several approaches to the localization of the structures of reaction intermediates or transition states. When the transferred ligand is an alcoolate chain, these structures are easily obtained using conventional methods of search of minima and transition states, that is chemical intuition. However, this becomes a major difficulty when the transfered ligand is an alkyl chain, for instance the methy transfer between zinc and copper. In order to handle this problem, we turned toward the global search algorithm of minima GSAM, based on the sampling of different topological structures from molecular fragments. This method, that had been successfully applied on atomic cluster or hydration of biological molecules, required adaptations for the study of organomtallic species. Once achieved, this algorithm has proved efficient for the study of reactions of experimental interest. Another transmetalation problem addressed is the determination of ligand transfer mechanism in a bimetallic complex having a weakly coordinating metal cation (Li) and a highly coordinating one (Cu). The electronic rearrangement associated with the transmetallation is determined through a trick which consist in replacing Li by a well coordinating atom such as hydrogen. This method was applied to the study dy of the inversion of configuration mechanism in a lithium allenylcuprate.

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