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Kleine Moleküle wie Treibhausgase, aber auch Distickstoff und Disauerstoff stehen im Fokus der chemischen Forschung. Solche Moleküle sind durch ihr Vorkommen in der Atmosphäre ubiquitär vorhanden, preiswert und könnten als Synthesebausteine für die Darstellung von komplexeren Molekülen verwendet werden. In dieser Arbeit wurde die Reaktion koordinativ ungesättigter Diketiminato-Nickelkomplexe ([LNi] Komplexe) mit kleinen Molekülen untersucht. Zunächst wurden die Mechanismen der N2-Aktivierung durch reduzierte [LtBuNiI]- und [LMe6NiI] Komplexe miteinander verglichen. Dabei konnte das distickstoffaktivierende Schlüsselintermediat identifiziert und strukturell charakterisiert werden. Weiter wurden die N2-Komplexe [(LtBuNiI)( 1 1 N2)] bzw. K2[(LtBuNiI)( 1 1 N2)], die Vorläufer für [LNiI]- und [LNi0]– Komplexfragmente darstellen, hinsichtlich ihrer Potentials zur Aktivierung der reaktionsträgen Treibhausgase SF6 und NF3 untersucht. Über Reaktionen von Übergangsmetallkomplexen mit NF3 war bis dahin noch nicht berichtet worden; zur Umsetzung von SF6 existierten wenige Publikationen, in denen aber sehr viele mechanistische Fragen offengeblieben sind. Die Mechanismen der SF6- und NF3-Aktivierung wurden durch Kombination einer Vielzahl von ex- und in situ Analysen beleuchtet. Im Falle der SF6 Aktivierung gelang es zudem, ein Nickel(I)-Intermediat zu isolieren. Ein Produkt beider Systeme war der Fluorido-Nickel(II)-Komplex [LtBuNiIIF], dessen Reaktionsverhalten ebenfalls studiert wurde. Doch nicht nur Komplexe mit Nickelatomen in niedrigen Oxidationsstufen erwiesen sich für die Aktivierung kleiner Moleküle geeignet, sondern auch kationische [LtBuNiII(D)]+-Komplexe. Diese Nickel(II)-Komplexe reagierten mit fluorierten Molekülen, N2O sowie O2, was bemerkenswert ist, da Nickel(II)-Komplexe üblicherweise inert gegenüber O2 sind. Im Zuge der O2-Studien wurde ein metastabiler Oranoperoxidkomplex isoliert und strukturell charakterisiert, was beispiellos in der Literatur ist. Current research focuses on the activation of small molecules like greenhouse gases, thermodynamically stable molecules like N2 and kinetically stabilized molecules like O2, which are all abundant in the atmosphere. Thus, it appears to be alluring to use them as cheap and readily available building blocks for the synthesis of value-added compounds. This dissertation deals with the reaction of low-coordinate diketiminate nickel complexes [LNi] and such small molecules. Initially, the mechanisms of the dinitrogen activation by reduced [LtBuNiI] and [LMe6NiI] complexes were studied. As a result, the key intermediate [(LtBuNiI)x(3 Br)xKx] (x > 1) was identified and structurally characterized. Subsequently, the nickel complexes [(LtBuNiI)( 1 1 N2)] and K2[(LtBuNiI)( 1 1 N2)], which represent sources for [LtBuNiI] and [LtBuNi0]– moieties, were applied to the activation of the inert, but very efficient greenhouse gases SF6 and NF3. Prior to these investigations, no transition metal complex had been reported to react with NF3. Publications dealing with the conversion of SF6 had been scarce, too, while at same time, the mechanisms involving its activation had been speculative. The mechanisms of the NF3 and SF6 activation reactions were deduced combining numerous ex-situ and in situ analytical methods. In case of the SF6 activation, even an intermediate could be isolated. In both systems, the nickel fluoride complex [LtBuNiIIF] was formed and its reaction behaviour was also studied. Furthermore, not only [LtBuNiI]- and [LtBuNi0]– moieties proved to be reactive towards small molecules, but also cationic [LtBuNiII(D)]+ complexes, which were specifically developed for this purpose. The reactions of [LtBuNiII(D)]+ complexes with fluorinated molecules (e. g. PhF, NF3), O2 and N2O were studied. In course of the O2 activation, a metastable organoperoxide complex was isolated and structurally characterized, which is unparalleled in the literature.

By employing silver salts with a weakly coordinating anion Ag[A] ([A]=[FAl{OC12F15}(3)], [Al{OC(CF3)(3)}(4)]), two phosphaalkynes could be coordinated side-on to a bare silver-(I) center to form the unprecedented homoleptic complexes [Ag(eta(2)-P equivalent to CtBu)(2)][FAl{OC12F15}(3)] (1) and [Ag(eta(2)-P equivalent to CtBu)(2)]-[Al{OC(CF3)(3)}(4)] (2). DFT calculations show that the perpendicular arrangement in 1 is the minimum energy structure of the coordination of the two phosphaalkynes to a silver atom, whereas for 2 a unique square-planar coordination mode of the phosphaalkynes at Ag+ was found. Reactions with donor molecules yield the trigonally planar coordinated silver salts [((CH3)(2)CO) Ag(eta(2)-P equivalent to CtBu)(2)][FAl{OC12F15}(3)] (3) and [(C7H8)(2)Ag(eta(2)-P equivalent to CtBu)][FAl{OC12F15}(3)] (4). All of the compounds were comprehensively characterized in solution and in the solid state.

Zirconaaziridinium inner sphere ion pairs (ISIPs) bearing alkyl chains of different lengths, [Cp2Zr(η2-CH2NR1R2)+···X−] (R1 = Me, R2 = C2H5, X− = MeB(C6F5)3−, ZrNC2BN; R1 = Me, R2 = C16H33, X− = MeB(C6F5)3−, ZrNC16BN; R1 = R2 = C18H37, X− = MeB(C6F5)3−, ZrNC18BN; R1 = Me, R2 = Ph, X− = MeB(C6F5)3−, ZrNPhBN; R1 = R2 = C18H37, X− = B(C6F5)4−, ZrNC18BT; R1 = Me, R2 = Ph, X− = B(C6F5)4−, ZrNPhBT), have been synthesized by the reaction of [Cp2ZrMe+···MeB(C6F5)3−] or [Cp2ZrMe+···B(C6F5)4−] with the suitable tertiary amine followed by selective C−H activation of one Me group of the coordinated amine and methane elimination. Subsequent reaction of ISIPs with THF afforded the corresponding outer-sphere ion pairs (OSIPs) ([ZrNC2THF][BN], [ZrNC16THF][BN], [ZrNC18THF][BN], [ZrNPhTHF][BN], [ZrNC18THF][BT], [ZrNPhTHF][BT]) in which the anion has been displaced into the second coordination sphere. The interionic structure in solution (i.e., the relative cation−anion position) and the self-aggregation level of both ISIPs...

An example for a process that can, in principle, be improved by the application of a catalyst is the synthesis of poly(2-methyl-propene)s (“polyisobutenes”), which are important for numerous industrial applications. Each year several 100,000 t are produced. The production of low-molecular weight polyisobutenes by means of cationic initiation by an excess of Lewis acids is well established. Typically, these initiators require the usage of solvents like chloroform, dichloromethane and ethylene and temperatures far below 0 °C (–100 °C in the case of ethylene as solvent). Solvent stabilized transition metal complexes with weakly coordinating counter anions overcome these drawbacks and thus are not only more efficient, but also more environmentally benign: they can be applied at ambient temperature and in non chlorinated solvents at low concentrations.

Description of the local microscopic structure in ionic liquids (ILs) is a prerequisite to obtain a comprehensive understanding of the influence of the nature of ions on the properties of ILs. The local structure is mainly determined by the spatial arrangement of the nearest neighboring ions. Therefore, the main interaction patterns in ILs, such as cation-anion H-bond-like motifs, cation-cation alkyl tail aggregation, and ring stacking, were considered within the framework of the nearest-neighbor approach with respect to each particular interaction site. We employed classical molecular dynamics (MD) simulations to study in detail the spatial, radial, and orientational relative distribution of ions in a set of imidazolium-based ILs, in which the 1-butyl-3-methylimidazolium (C4mim+) cation is coupled with the acetate (OAc-), chloride (Cl-), tetrafluoroborate (BF4-), hexafluorophosphate (PF6-), trifluoromethanesulfonate (TfO-), or bis(trifluoromethanesulfonyl)amide (TFSA-) anion. It was established that several structural properties are strongly anion-specific, while some can be treated as universally applicable to ILs, regardless of the nature of the anion. Namely, strongly basic anions, such as OAc- and Cl-, prefer to be located in the imidazolium ring plane next to the C-H2/4-5 sites. By contrast, the other four bulky and weakly coordinating anions tend to occupy positions above/below the plane. Similarly, the H-bond-like interactions involving the H2 site are found to be particularly enhanced in comparison with the ones at H4-5 in the case of asymmetric and/or more basic anions (C4mimOAc, C4mimCl, C4mimTfO, and C4mimTFSA), in accordance with recent spectroscopic and theoretical findings. Other IL-specific details related to the multiple H-bond-like binding and cation stacking issues are also discussed in this paper. The secondary H-bonding of anions with the alkyl hydrogen atoms of cations as well as the cation-cation alkyl chain aggregation turned out to be poorly sensitive to the nature of the anion.

Although the cyclo-P6 complex [(Cp*Mo)2 (μ,η(6) :η(6) -P6 )] (1) was reported 30 years ago, little is known about its chemistry. Herein, we report a high-yielding synthesis of 1, the complex 2, which contains an unprecedented cyclo-P10 ligand, and the reactivity of 1 towards the "naked" cations Cu(+) , Ag(+) , and Tl(+) . Besides the formation of the single oxidation products 3 a,b which have a bisallylic distorted cyclo-P6 middle deck, the [M(1)2 ](+) complexes are described which show distorted square-planar (M=Cu(4 a), Ag(4 b)) or distorted tetrahedral coordinated (M=Cu(5)) M(+) cations. The choice of solvent enabled control over the reaction outcome for Cu(+) , as proved by powder XRD and supported by DFT calculations. The reaction with Tl(+) affords a layered two-dimensional coordination network in the solid state.

Crystallization from methanol solutions resulted in new supramolecular complexes of a flexible polyamine receptor N, N′-3-azapentane-1, 5-bisij3-IJ1-aminoethylidene)-6-methyl-3H-pyran-2, 4-dione] (L) with spherical (Br− and I−), linear (SCN−) or pyramidal (ClO3−) anions. The recognition and self-assembly processes yielded five solids: solvated (1a) and non-solvated (1b) forms of HL : SCN− complex with quite different receptor conformations, a supramolecular complex with ClO3− anion (3), which is isoskeletal to 1b, and HL : Br− (2) and HL : I− complexes which are isoskeletal to 1a. It is shown that the rich coordinating potential of the anions investigated arises not only from their geometry but also from their ambivalent accepting functionalities. The divergence in the way binding occurs is reflected on supramolecular synthons stabilizing crystal structures as well as on the physicochemical properties of the obtained solids. In these systems, anion binding could be interpreted as a competition between two “solvation spheres”, one provided by the solvent molecules and the other dominated by high-order supramolecular receptors built from HL molecules. This behaviour is related to previously reported complexes of HL with trigonal, tetrahedral and octahedral anions, emphasizing the receptor's conformational adaptability for providing the most favourable surrounding for guest inclusion in the rigid environment of a crystal.

In this work, a fundamental study of ionic liquids (ILs) is shown. The main goal was to establish relationships between rheological and tribological properties of ILs and to understand how these properties are linked to the molecular structure of ILs. Of particular interest were the effects occurring to a frictional system due to variations of the anions and the alkyl chain length of the imidazolium-based cations. Tribological experiments were performed using a reciprocating ball-on-disc test machine. To understand the effects resulting from a variation of the structural characteristics of the used ILs on the rheological properties, studies were performed using a rheometer. The results obtained are very promising in terms of improving friction and wear behaviour by using ILs as lubricants.

Chlorocarbon solvents (solv=CH(2)Cl(2), CHCl(3)) are suggested to play an active role in the oxidative addition of halogens, X(2) (X=Cl, Br, I), to homoleptic d(8) perfluoromethyl and -phenyl platinum(II) species [Pt(R(F))(4)](2-) (R(F)=CF(3), C(6)F(5)). The perfluoromethyl group, CF(3), has been found to be considerably less prone to undergo reductive elimination processes, and is, therefore, more suitable for stabilizing organoplatinum(IV) derivatives (see scheme).The equilibrium geometries of the homoleptic perfluorinated organoplatinate(II) anions [Pt(CF(3))(4)](2-) and [Pt(C(6)F(5))(4)](2-) have been computed at the B3P86/LANL2DZ level of theory. Remarkably good agreement with the experimentally determined structures has been obtained by X-ray diffraction methods. The reactivity of [NBu(4)](2)[Pt(CF(3))(4)] (1) towards halogens (Cl(2), Br(2), and I(2)) has been investigated by using a combined experimental and theoretical approach. The perfluoromethyl derivative 1 has been found to undergo clean oxidative addition of the three halogens under investigation, giving rise to [NBu(4)](2)[trans-Pt(CF(3))(4)X(2)] (X=Cl (7), Br (10), I (13)) in a quantitative and stereoselective way. In the low-temperature reaction of the perfluorophenyl derivative [NBu(4)](2)[Pt(C(6)F(5))(4)] (3) with Cl(2) or Br(2), the corresponding oxidative-addition products [NBu(4)](2)[trans-Pt(C(6)F(5))(4)X(2)] (X=Cl (14), Br (15)) can also be obtained. In the case in which X=Br and working in CHCl(3) at -55 degrees C, it has been possible to detect the formation of an intermediate species to which we assign the formula [trans-Pt(C(6)F(5))(4)Br(ClCHCl(2))](-) (16). The solvento complex 16 is thermally unstable and prone to undergo reductive elimination of C(6)F(5)--C(6)F(5). In the presence of PhCN, complex [NBu(4)][trans-Pt(C(6)F(5))(4)Br(NCPh)] (17) was isolated and structurally characterized. The reaction of 3 with I(2) gave no organoplatinum(IV) compound. Our comparative study reveals that the CF(3) group is especially suited to stabilize organometallic compounds in high oxidation states. This ability can be attributed to a combination of factors: its hardness, its high group electronegativity, its small size, and its reluctance to undergo reductive elimination processes.

Acid remarks: The anhydrous diprotic boron acids H(2)(B(12)X(12)) (X = Cl, Br; see picture, B orange, X green) are the first examples of diprotic superacids and may be the strongest acids yet isolated. Both protons protonate benzene to give benzenium ion salts that are stable at room temperature. These acids owe their existence to the stability of the icosahedral B(12) cluster with its dinegative charge buried beneath a layer of halide substituents.

Die Synthese und Anwendung schwach koordinierender Anionen ist Thema dieser Arbeit. Im ersten Teil wird über die Darstellung von Salzen mit dem Tetracyanoborat-Anion [B(CN)4]- berichtet und im zweiten Teil die Synthese der perfluorierten closo-Carborat-Anionen des Typs [1-R-CB11F11]- sowie ihre Verwendung zur Stabilisierung sehr elektrophiler Kationen beschrieben. Die freie Tetracyanoborsäure H[B(CN)4] sowie die entsprechenden Hydrate [H3O][B(CN)4] und [H5O2][B(CN)4] sind ebenfalls Gegenstand der Untersuchungen. Desweiteren werden neue Salze des [B(CN)4]--Anions mit zweiwertigen Kationen synthetisiert und eingehend spektroskopisch sowie strukturell charakterisiert. Im Gegensatz zu den zuvor bekannten aufwendigen und mehrstufigen Synthesen des Cs[CB11H12] erfordert die neue über eine Dichlorcarben-Insertion in den nido-[B11H14]--Cluster verlaufende Zwei-Stufen-Synthese einen präparativ wesentlich geringeren Aufwand. In dieser Arbeit konnte die Syntheseroute optimiert werden, so dass das Dodecahydro-1-carba-closo-dodecaborat ohne Nebenprodukte entsteht. Die anschließende Fluorierung und Derivatisierung der Stammverbindung [CB11H12]- führt zu den sehr schwach koordinierenden Anionen [1-R-CB11F11]- mit R = H, Alkyl. Ausgehend von diesen Cs-Salzen gelingt es, über die Zwischenstufe der [C(C6H5)3]+-Salze die neuen sehr elektrophilen und extrem reaktiven Trimethylsilyl-Kationen mit den Anionen [1-H-CB11F11]- und [1-C2H5-CB11F11]- zu stabilisieren. Die thermisch stabilen Salze [(CH3)3Si][1-H-CB11F11] und [(CH3)3Si][1-C2H5-CB11F11] werden umfassend durch Einkristallstrukturanalysen, NMR-Spektroskopie, Schwingungs-spektroskopie owie durch thermische Analyse charakterisiert. Bei der Verbindung [(CH3)3Si][1-H-CB11F11] handelt es sich um eine Ionische Flüssigkeit, da diese einen Schmelzpunkt von 80 °C aufweist und die Schmelze elektrische leitend ist. Ebenfalls zum ersten Mal werden ausgehend von den Silyl-Salzen die freien Brønstedt-Supersäuren H[1-H-CB11F11] und H[1-C2H5-CB11F11] dargestellt und charakterisiert. Außerdem wird in dieser Arbeit die Reaktivität dieser festen Supersäuren gegenüber unterschiedlichen Verbindungen untersucht. Im Rahmen dieser Arbeit konnte das Potential der schwach koordinierenden Anionen [B(CN)4]- und [1-R-CB11F11]- (R = H, Alkyl) anhand der Synthese neuer Verbindungen sowie der Stabilisierung reaktiver Kationen gezeigt werden. The aim of this thesis is the synthesis and application of weakly coordinating anions (WCA). In the first part the preparation of salts containing tetracyanoborate ([B(CN)4]-) anions is discussed. In part two the synthesis of perfluorinated closo carborane anions of the type [1-R-CB11F11]- as well as their use in stabilizing highly electrophilic cations is described. The tetracyanoborate acid H[B(CN)4] as well as the hydrates [H3O][B(CN)4] and [H5O2][B(CN)4] are also discussed. In addition, new salts of [B(CN)4]- anions with various divalent cations are prepared and characterized by spectroscopic methods as well as X-ray crystallography. Contrary to the former multi-step syntheses of Cs[CB11H12] the new two-step synthesis via dichlorocarbene insertion of [B11H14]- requires significant less effort of preparative chemistry. In this thesis the optimized synthetic route for the preparation of pure dodecahydro-1-carba-closo-dodecaborane is described. Fluorination and derivatization of Cs[CB11H12] gives the cesium salts Cs[1-R-CB11F11] with R = H, alkyl. Starting from these compounds it is possible to stabilize highly reactive trimethylsilyl cations via intermediate trityl salts. The thermally stable salts [(CH3)3Si][1-H-CB11F11] and [(CH3)3Si][1-C2H5-CB11F11] are fully characterized by X-ray diffraction, NMR spectroscopy, vibrational spectroscopy as well as thermal analysis. It is shown that the compound [(CH3)3Si][1-H-CB11F11] acts as ionic liquid because the melting point is 80 °C and the liquid is an electric conductor. Starting from these silyl salts the free Brønstedt super acids H[1-H-CB11F11] and H[1-C2H5-CB11F11] are also synthesized and characterized for the first time. Furthermore the reactions of these solid super acids with a variety of different compounds are studied. The synthetic potential of the weakly coordinating anions [B(CN)4]- and [1-R-CB11F11]- (R = H, alkyl) could be demonstrated by the preparation of various new compounds and by their stabilizing effect on reactive cations.

Pentaphosphaferrocene coordinates as a ligand to the large monocation Tl+. In addition, one of the phosphorus atoms of each cyclo-P5 moiety coordinates to a neighboring Tl+ ion to give a one-dimensional polymer. Even at low temperatures, fast rotation of the P5 rings is observed in solution and in the solid state.

The first solid-state structures of complexed P3N3X6 (X = halogen) are reported for X = Cl. The compounds were obtained from P3N3Cl6 and Ag[Al(OR)4] salts in CH2Cl2/CS2 solution. The very weakly coordinating anion with R = C(CF3)3 led to the salt Ag(P3N3Cl6)2+[Al(OR)4]- (1), but the more strongly coordinating anion with R' = C(CH3)(CF3)2 gave the molecular adduct (P3N3Cl6)AgAl(OR')4 (3). Crystals of [Ag(CH2Cl2)(P3N3Cl6)2]+[Al(OR)4]- (2), in which Ag+ is coordinated by two phosphazene and one CH2Cl2 ligands, were isolated from CH2Cl2 solution. The three compounds were characterized by their X-ray structures, and 1 and 3 also by NMR and vibrational spectroscopy. Solution and solid-state 31P NMR investigations in combination with quantum chemically calculated chemical shifts show that the 31P NMR shifts of free and silver-coordinated P3N3Cl6 differ by less than 3 ppm and indicate a very weakly bound P3N3Cl6 ligand in 1. The experimental silver ion affinity (SIA) of the phosphazene ligand was derived from the solid-state structure of 3. The SIA shows that (PNCl2)3 is only a slightly stronger Lewis base than P4 and CH2Cl2, while other ligands such as S8, P4S3, toluene, and 1,2-Cl2C2H4 are far stronger ligands towards the silver cation. The energetics of the complexes were assessed with inclusion of entropic, thermal, and solvation contributions (MP2/TZVPP, COSMO). The formation of the cations in 1, 2, and 3 was calculated to be exergonic by delta(r)G(degrees)(CH2Cl2) = -97, -107, and -27 kJ mol(-1), respectively. All prepared complexes are thermally stable; formation of P3N3Cl5+ and AgCl was not observed, even at 60 degrees C in an ultrasonic bath. Therefore, the formation of P3N3Cl5+ was investigated by quantum chemical calculations. Other possible reaction pathways that could lead to the successful preparation of P3N3X5+ salts were defined.

During the last decades, weakly coordinating anions (WCAs) have become a field of great interest both in basic and applied chemistry, as – if compared to "normal" classical anions like Cl- or SO42- – they have a lot of unique and unusual properties, such as high solubility in low dielectric media (like CH2Cl2 or toluene), "pseudo gas phase conditions" in condensed phases and the stabilization of strong electrophilic cations as well as of weakly bound and low charged complexes. Within the present thesis, several contributions to the chemistry of WCAs were made: Based on quantum chemical calculations, the stability of the most widely used WCAs have been investigated, using parameters such as the fluoride ion affinity (FIA), partial charges or frontier orbital energies. One class of the WCAs, the poly- and perfluorinated alkoxyaluminates of the type [Al(ORF)4]- and [(RFO)3Al-F-Al(ORF)3]-, has been used to investigate weakly bound Ag(P4S3) Lewis acid-base adducts and electrophilic cations: When the silver salts of fluorinated alkoxyaluminates are reacted with P4S3, different structure types are found for the adducts, depending on the anion used. The dynamics of these complexes has been explored by different spectroscopic methods (IR, Raman, MAS-NMR, NMR in solution) and X-ray diffraction. The first structurally characterized trihalocarbenium ions CI3+ as salts of different aluminates have been prepared and fully characterized using various spectroscopic techniques, e.g. NMR and vibrational spectroscopy, as well as single-crystal diffraction. The Lewis acidities of the halocarbenium ions have been investigated both on experimental and theoretical grounds and they have been compared to those of the isoelectronic haloboranes. The NO2+ salt of the [Al(OC(CF3)3)4]- anion has been synthesized by a metathesis reaction. It has been reacted with P4 in order to obtain naked phosphorus cations Px+. Another project was the synthesis and characterization of the tetraalkylammonium salts of the [Al(ORF)4]- anions, a promising class of substances for the use in electrochemical applications in non-polar solvents. All subjects treated experimentally within this thesis have been accompanied by quantum chemical calculations.

The superweak tetrakis(nonafluoro-tert-butoxy)aluminate coordinating anion was employed to introduce pseudo-gas-phase conditions to the 2-[5-(1,3-dihydro-1,3,3-trimethyl-2H-indol-2-ylidene)-1,3-pentadien-1-yl]-1,3,3-trimethyl-3H-indolium chromophore. The resulting formation of a photoactive organic-inorganic hybrid salt has led to a highly stabilized excited state of the organic chromophore mainly due to the minimized lattice energy and Coulomb interactions. These highly beneficial features caused by the well dispersed negative charge of the anion have led to an enhanced neat spin-casted film fluorescence intensity, prolonged fluorescence lifetime, smooth thin film surfaces and a record power photovoltaic efficiency of 3.8 % when compared to organic salts of this particular chromophore containing anions with localised negative charge. Clear evidence is given that a superweak coordinating anion is an emerging key parameter in cyanine dye photochemistry. This approach can be seen as a general guideline to prepare highly efficient ionic dyes for organic semiconductor applications.

Cyanine dyes represent a class of ionic functional materials used by a broad heterogeneous science community contain-ing biologists, chemists, physicists and materials scientists. Their diverse application opportunities are ranging from fluorescence markers, nonlinear optics, CD-R data storage, photography and organic electronics. Therefore the development of cyanine dyes and their applications in chemistry, engineering, medicine and pharmacology is growing continuously. A typical leitmotif of a cyanine dye contains two nitrogen heterocyclic rings joined by a conjugated chain of carbon atoms. Due to the synthetic approach, quaternary salt precursors are required resulting in ionic compounds. Such chromophores are positively charged and require a counter anion to maintain the overall charge neutrality. Several reports were presenting certain anions as efficiency enhancers in cyanine dye based organic electronic devices. Despite their long presence in science, there is a lack of knowledge behind the mechanisms causing these efficiency enhancements. Furthermore, in the field of organic electronics, the processability of cyanine dyes towards electronic devices was restricted to solution-based methods. In the present thesis work the three main challenges in cyanine dye research, namely: efficient ion exchange procedures, mechanisms behind organic electronics figures of merit enhancement as well as the introduction of physical vapour deposition method have been addressed. An efficient halide-for-anion exchange method with the potential for industry scale up was introduced. This allowed modifying a cationic cyanine chromophore with organic or inorganic anions yielding six salts. The following investigations of these six anions by either varying organic moieties or negative charge delocalisation paved the way towards a generalized concept describing the semiconducting properties of this cationic cyanine chromophore. The lattice energy was established as a universal parameter describing cyanine salt semiconducting properties on a universal energy scale. Such decoupling of an ionic structure from its Lewis formula allows future predictions of semiconducting properties which can be widened to all organic ionic functional materials. Furthermore weakly coordinating anion influence on the volatility of a cyanine chromophore established physical vapour deposition as thin film fabrication method. Using co-evaporation of the cyanine dye and the fullerene C60 a suitable bulk heterojunction morphology was obtained. This resulted in the fabrication of the first fully vacuum deposited cyanine dye bulk heterojunction device.