Lehrstühle für Anorganische Chemie
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Item Coinage metal complexes for near infrared emission and energy transfer photocatalysis(2024) Maity, Sabyasachi; Steffen, Andreas; Henke, SebastianHerein I present comprehensive studies on synthesis, structure, and photophysical behavior of a series of luminescent CuI phosphide (-PPh2) complexes supported by various mono- and bidentate phosphines displaying TADF behaviour. Depending upon the stoichiometry used two heteroleptic dimers and four heteroleptic polynuclear CuI clusters could be isolated from the self-assembly reaction of CuI-phosphide and phosphine ligand. These complexes are green-to-red (1-2 & 4-6) and NIR (3) photo-emitters with emission maxima varying over the range λmax = 515 to 890 nm. Moderate to high photoluminescence quantum yield (Ф = 20-44% ), with a relatively high radiative rate constant of up to 3 × 10^6 s^-1, and short lifetimes τ = 0.1-34 μs were observed. Compounds 2 and 5 exhibit pronounced thermochromism and evidence of dual TADF behaviour originating from two different types of excited states. I also report a new sterically demanding, electrophilic [2.2]isoindolinophanyl-based carbene (iPC) that bears a [2.2]paracyclophane moiety. The iPC ligand is a very potent π-chromophore, which participates in low energy IL-“through-space”-CT transitions in [Au(iPC)2]OTf (8) in the visible. The steric demand of the iPC leads to a high stability of 8 against air, moisture, or solvent attack, and ultralong-lived green phosphorescence with a lifetime of 185 μs is observed in solution. The beneficial photophysical and electronic properties of the iPC ligand, including a large accessible π surface area, were exploited by employing highly efficient energy transfer (EnT) photocatalysis in a [2+2] styrene cycloaddition reaction using 8, which outperformed other established photocatalysts in comparison. In addition I also describe a series of linear copper(I) carbene carbazolate complexes (9-12) bearing the [2.2]isoindolino-phanyl-based carbene (iPC) ligand as a potent excited state π-acceptor. The compounds show efficient TADF from ligand-to-ligand charge transfer (1/3LLCT) states with quantum yields of up to 0.8 and exceptional kr of 0.8-1.9×10^6 s^-1 that are among the fastest for CuI emitters, outcompeting traditional triplet emitters based on Ir^III and Pt^II.Item Towards fast circularly polarized luminescence in 2‐coordinate chiral mechanochromic copper(I) carbene complexes(2023-06-05) Muthig, André M. T.; Wieland, Justin; Lenczyk, Carsten; Koop, Stefan; Tessarolo, Jacopo; Clever, Guido H.; Hupp, Benjamin; Steffen, AndreasA series of chiral mechanochromic copper(I) cAAC (cAAC=cyclic (alkyl)(amino)carbene) complexes with a variety of amide ligands have been studied with regard to their photophysical and chiroptical properties to elucidate structure-property relationships for the design of efficient triplet exciton emitters exhibiting circularly polarized luminescence. Depending on the environment, which determines the excited state energies, either thermally activated delayed fluorescence (TADF) from 1/3LLCT states or phosphorescence from 3LLCT/LC states occurs. However, neither chiral moieties at the carbene nor at the carbazolate ligands provide detectable luminescence dissymmetries glum. An exception is [Cu(phenoxazinyl)(cAAC)], showing orange to deep red TADF with λmax=601–715 nm in solution, powders and in PMMA. In this case, the amide ligand can undergo distortions in the excited state. This design motif leads to the first linear, non-aggregated CPL-active copper(I) complex with glum of −3.4 ⋅ 10−3 combined with a high radiative rate constant of 6.7 ⋅ 105 s−1.Item Multi-cage systems and dynamic transformations(2024) Benchimol, Elie; Clever, Guido H.; Ribas, XavisBiological systems use multi-component low-symmetry receptors with dynamic structures operating in networks far from equilibrium to perform complex functions. While coordination cages have taken great inspiration from the structure of these receptors by harnessing their cavities, the use of their dynamic nature and function is still in its infancy. The introduction of heteroleptic cages has brought the possibility of forming low-symmetry assemblies but also of going towards multi-functional species. However, several of the previously described features are missing to this day in order to get closer to biological complexity and function. Hence, this thesis aims to introduce a new concept in the field: multi-cage systems. The complexity does not only arise anymore from the number of components in a single assembly but from the number of discernable assemblies and their structure within a population of cages. A new type of self-sorting namely heteromeric completive self-sorting is coined and defines cage populations where multiple heteroleptic structures coexist orthogonally. This is further extended to the creation of cage systems in which heteroleptic and homoleptic hosts coexist. This concept allows a further step towards mimicking biological systems as it enables the possibility of both intramolecular and intermolecular transmission of information. Multiple coexisting assemblies can in theory perform orthogonal, cooperative or antagonist functions opening new avenues for the applications of cages in systems chemistry. The proof of concept of multi-cage systems is introduced by taking advantage of a singular diketopyrrolopyrrole (DPP) ligand, which can adopt distinct conformations and thus offers the possibility of forming coexisting cages with different topologies. One of these topologies is the trans-figure-of-eight Pd2A2B2 heteroleptic structure and is central to most of the results of the thesis. The two DPP ligands form the eight by adopting an S shape conformation and interlacing in the middle of the assemblies, occupying the cavity. It allows a precise arrangement of ligands, giving also robust heteroleptic cages, and owns an inherent chirality as the “8” can adopt P or M chirality. Not only this ligand is fostered for its structure and variability of conformation but it is also a well-known dye with strong luminescence. Therefore, we demonstrate its use for the emergence of a new multi-cage self-sorting as well as its utilization for the formation of single multi-chromophore assemblies with outstanding photophysical properties thanks to intramolecular energy transfer. A second system presenting the premises of functionality is then introduced. Taking advantage of guest affinity, we show that an increase in the number of components of a system results in the simplification of its self-sorting outcome. This can be seen as a case of “simplexity”. A heteroleptic cage can eventually coexist with a homoleptic host-guest complex and subsequently uptake another anionic guest orthogonally to the first binding event. This is defined as guest segregation in a multi-cage system and differs from the classical narcissistic self-sorting. Further harnessing the slight guest affinity for one of the homoleptic species finally allows the creation of a system where three host-guest complexes coexist orthogonally without shuffling their components or guests. Eventually, the concept of cage population is extended to dynamic mixtures in which competition for resources between components allows the emergence of chiral memory and out-of-equilibrium phenomenon. We use a chiral ligand derived from the Tröger base structure to both induce chirality on pristine fullerene C60 and C70 and drive the formation of a unique chiral diastereoisomer of the figure-of-eight species. Because of the high affinity of this ligand to form a host-guest complex with fullerene, it is then possible to create a transformable multi-cage system in which the chiral figure-eight ‘releases’ its outer ligands and exchanges them for non-chiral ones. However, we still observe a chiral answer in circular dichroism witnessing the (partial) retention of chirality of the central “8” created by the DPP ligands. We then take advantage of the differences in both thermodynamic and kinetic behaviors to drive the transformative system out of equilibrium and demonstrate the transient formation of the chiral figure-eight before its decay to reform the thermodynamically preferred complex with fullerene. This thesis introduces the concept of populations, networks, segregated functions, and transformative out-of-equilibrium behavior in the field of cages.Item Engineering soluble diketopyrrolopyrrole chromophore stacks from a series of Pd(II)‐based ravels(2023-07-17) Regeni, Irene; Chowdhury, Rituparno; Terlinden, Kai; Horiuchi, Shinnosuke; Holstein, Julian J.; Feldmann, Sascha; Clever, Guido H.A strategy to engineer the stacking of diketopyrrolopyrrole (DPP) dyes based on non-statistical metallosupramolecular self-assembly is introduced. For this, the DPP backbone is equipped with nitrogen-based donors that allow for different discrete assemblies to be formed upon the addition of Pd(II), distinguished by the number of π-stacked chromophores. A Pd3L6 three-ring, a heteroleptic Pd2L2L′2 ravel composed of two crossing DPPs (flanked by two carbazoles), and two unprecedented self-penetrated motifs (a Pd2L3 triple and a Pd2L4 quadruple stack), were obtained and systematically investigated. With increasing counts of stacked chromophores, UV/Vis absorptions red-shift and emission intensities decrease, except for compound Pd2L2L′2, which stands out with an exceptional photoluminescence quantum yield of 51 %. This is extraordinary for open-shell metal containing assemblies and explainable by an intra-assembly FRET process. The modular design and synthesis of soluble multi-chromophore building blocks offers the potential for the preparation of nanodevices and materials with applications in sensing, photo-redox catalysis and optics.Item Chiroptical recognition of carboxylates with charge‐neutral double‐stranded zinc(II) helicates(2023-07-30) Kalarikkal, Malavika G.; Drechsler, Christoph; Tusha, Gers; Schäfer, Lars V.; Van Craen, DavidChirality analysis of small molecules for the determination of their enantiopurity is nowadays ruled by streamlined chromatographic methods which utilize chiral stationary phases. Chiroptical probes which rely on host–guest interactions are so far overshadowed by the latter but have the benefit of depending only on common spectroscopic techniques such as CD spectroscopy to distinguish enantiomers and to quantify their ratio. Interest into this receptor-based approach is constantly rising because non-invasive high-throughput screenings with a minimal waste production can be performed. In this study we investigate the possibility to utilize metal-based containers in form of charge-neutral helicates able to recognize anions for this purpose. Key building block of the helicates are triazole units which show rotational freedom and give rise to either a meso-structure or a racemic mixture of the right- and left-handed complex. A chiroptical response of the probe is observed upon recognition of chiral mono- or dicarboxylates and chirality analysis of tartrate is conducted by CD spectroscopy.Item Complex systems based on coordination cages(2024) Drechsler, Christoph; Clever, Guido H.; Kast, Stefan M.Koordinationskäfige entstehen durch die Kombination von bis-monodentaten organischen Liganden und Metallkationen. In unserer Gruppe konzentrieren wir uns auf laternenförmige PdII2L4-Spezies, wobei L ein gebogener, bis-monodentater Ligand ist. Diese Käfige haben vier Öffnungen, in die kleine, meist anionische, gastähnliche Moleküle passen. Die Systemchemie befasst sich mit komplexen chemischen Mischungen, die biologische Systeme nachahmen sollen. Koordinationskäfige, die Enzymen ähneln, können dabei helfen, da sie durch dynamische Koordinationsbindungen und flexibles Gastverhalten anpassungsfähig sind. Die zunehmende Komplexität solcher Systeme stellt die Analytik vor Herausforderungen. Die Massenspektrometrie, insbesondere in Kombination mit der Ionenmobilitätsspektrometrie, ist ein wertvolles Werkzeug zur Untersuchung komplexer Mischungen. Im ersten Teil dieser Arbeit wird die Trapped Ion Mobility Spectrometry verwendet, um die Struktur von Palladium(II)-Koordinationskäfigen zu untersuchen. Die experimentell ermittelte Ionenmobilität K wird in den Kollisionsquerschnitt umgewandelt. Für die theoretische Untersuchung wird ein in silico Modell des Koordinationskäfigs entweder geometrisch optimiert oder in einer kurzen Molekulardynamik-Simulation verwendet. Der theoretische Kollisionsquerschnitt wird dann mit dem experimentellen Wert verglichen, um die Übereinstimmung zu überprüfen. Ein besonderes Augenmerk liegt auf den flexiblen Eigenschaften von Alkylseitenketten, die Fehler in der Querschnittsberechnung verursachen können. Daher wurde eine Reihe von Käfigen mit unterschiedlich langen Seitenketten synthetisiert, gemessen und verglichen. Diese Ergebnisse geben Aufschluss über das Verhalten dieser Seitenketten in der Gasphase, wobei die London-Dispersionskräfte eine wichtige Rolle spielen. Solche Dispersionskräfte können Kompaktierungen der Käfige in der Gasphase verursachen. Im zweiten Teil der Arbeit werden komplexe Mischungen von Käfigen mit photoschaltbaren Einheiten untersucht. Heteroleptische Käfige mit photoschaltbaren Dithienylethen (DTE)-Einheiten wurden synthetisiert und charakterisiert. Durch Bestrahlungsexperimente konnten verschiedene Käfigmischungen mit unterschiedlicher Komplexität erzeugt werden. Im dritten Teil wird die langsame Bildung von doppelt verschränkten Käfigen untersucht. Dabei dient der monomere Käfig mit großem Hohlraum als vorübergehende Kapsel für ein großes Gastmolekül. Dieses Konzept der transienten Gastbindung wird hinsichtlich seiner Eigenschaften und Grenzen erforscht.Item Chromophoric coordination cages(2024) Walther, Alexandre; Clever, Guido H.; Lützen, ArneOne of the principal reasons for the extensive study of coordination cages in the last few decades is the promise they hold for their use as artificial analogues to biological systems, and more specifically artificial enzymes. Indeed, like this class of catalytically active proteins, coordination cages and capsules possess a central cavity able to bind guest molecules. In turn, it has been shown by the supramolecular community that catalytic processes can happen in coordination cages, by the specific arrangement of guest molecules in the cavity. However, unlike enzymes, coordination cages have been seen as rather conformationally or topologically static, in contrast to the vast changes ternary and quaternary structure that may take place upon the binding of a substrate to an enzyme. Moreover, the cavity of non-chiral homoleptic coordination cages do not allow for the asymmetric catalysis enabled by the chirotopic and low-symmetry catalytic pocket of enzymes. Therefore, to better mimic biological systems with coordination cages, the study of low-symmetry systems that are responsive to external stimuli is of interest. In the first project of this thesis, I present an azulene-based Pd2L4 lantern-shaped cage that transforms into a Pd4L8 tetrahedral complex upon addition of benzene disulfonate guests. This geometrical change is clean, efficient, and rapid. The final structure was determined by single crystal X-ray crystallography. The use of azulene, a simple, but coloured two-ring aromatic hydrocarbon allows for an easy monitoring of the progress of the transformation by eye only. Using a second coordination cage based on methylene blue, the transformation was shown to be reversible, thanks to the transfer of the guest from the tetrahedron to the newly added cage, which has a higher affinity for the disulfonates. This experiment demonstrates several key principles of advanced coordination cage chemistry, such as multi-component non-statistical systems of narcissistically self-sorting cages, or guest transfer. Several other azulene-based ligands were synthesised as well, but none of their corresponding homoleptic assemblies could undergo the same cage-to-cage transformation, highlighting the sensitivity of the first system to shape and size. A second azulene-based family of ligands was prepared next, but this time with a chiral amino-biazulene backbone, isomeric to the widely adopted BINOL moiety. Two ligands were thus synthesised, the first of them bearing two pyridine donor groups. Using the racemate of the first ligand for the formation of the Pd(II)-cage ultimately resulted in the formation of a single meso-trans isomer of the Pd2L4 cage in acetonitrile and DMSO, instead of a statistical mixture. X-ray structure analysis of the cage unexpectedly revealed that discrete solvent molecules were responsible for the non-statistical arrangement, by acting as tethers between the amino groups of the ligands, through hydrogen bonding. This is the first time that single solvent molecules were shown to directly influence the outcome of the chiral self-sorting of a coordination cage. This observation was supplemented with experimental and computational models. A larger ligand with 7-isoquinoline groups was also synthesised. Due to the larger donor groups, the amino groups are pulled further away from each-other in the final coordination assembly. This greater distance means that the solvent molecules were not able to bridge the ligands anymore, and therefore a statistical mixture was observed in this case. Finally, thiophene- and and thieno[3,4b]pyrazine-based ligands were used to potentially recreate the cage-to-tetrahedron transformation described in the first part. The transformation was successful due to the similar geometry imparted by the five-membered rings. In addition, the thieno[3,4b]pyrazine-based ligands were observed to be highly luminescent, and the resulting Pd2L4 cages were as well. This is an interesting result, as the fluorescence of palladium(II) assemblies are generally quenched, and therefore their use as fluorescent probes can be limited. Moreover, the emission colour of those ligands could be modulated by electron withdrawing or donating substituents.Item Modulation of porosity, melting and glass formation in zeolitic imidazolate frameworks(2024) Xue, Wenlong; Henke, Sebastian; Clever, GuidoThe phase transition of metal–organic frameworks (MOFs) from a crystalline to a liquid and a glassy state represents a promising avenue for the development of a novel class of amorphous materials. In contrast to their crystalline counterparts, liquid and glassy MOFs exhibit excellent processability, a highly advantageous property for industrial applications where the formation of specific shapes, such as pellets or thin films, is often a prerequisite. Furthermore, unlike conventional glasses, the utilization of coordination chemistry allows for the implementation of rational design concepts, thereby facilitating the fine-tuning of the desired properties. In this thesis, Solvent-assisted linker exchange (SALE) as a versatile method for the preparation of melt-quenched MOF glasses from proto typical MOFs, such as ZIF-8. Two additional organic linkers are incorporated into the non-meltable ZIF-8, yielding high-entropy linker-exchanged ZIF-8 derivatives that undergo a phase transition from crystalline to liquid and glassy states upon thermal treatment. This strategy opens new pathways for creating meltable and glass-forming MOFs from the extensive pool of non-meltable MOFs documented in the literature. Moreover, Post-synthetic ball-milling (PSBM) is explored as a suitable alternative to melt-quenching in MOF glass formation. MOFs can be transformed into glasses in just 5 minutes by mechanical milling at room temperature. This PSBM method can also transform crystalline MOFs in the glassy state that do not melt due to low thermal stability. This approach broadens the spectrum of potential applications, paving the way for the development of multifunctional MOF glass composites and expanding their use into more diverse fields. Additionally, Single-component glass-ceramics (SCGC) explored from a Cd-based MOF exhibit unique structural and thermal properties. Upon reheating the Cd-based MOF glass, it undergoes partial recrystallization into a single component glass-ceramic state with potentially enhanced mechanical properties — a feature not observed in previous melt-quenched MOF glasses. Overall, this thesis offers new insights into the porosity of MOF glasses, their formation mechanism, the preparation of MOF glass-ceramics and a generic method for the mechanochemical preparation of MOF glasses.Item Highly porous metal-organic framework liquids and glasses via a solvent-assisted linker exchange strategy of ZIF-8(2024-05-24) Xue, Wen-Long; Kolodzeiski, Pascal; Aucharova, Hanna; Vasa, Suresh; Koutsianos, Athanasios; Pallach, Roman; Song, Jianbo; Frentzel-Beyme, Louis; Linser, Rasmus; Henke, SebastianBy combining the porosity of crystalline metal-organic frameworks (MOFs) with the unique processability of the liquid state, melt-quenched MOF glasses offer exciting opportunities for molecular separation. However, progress in this field is limited by two factors. Firstly, only very few MOFsmelt at elevated temperatures and transform into stable glasses upon cooling the correspondingMOF liquid. Secondly, theMOF glasses obtained thus far feature only very small porosities and very small pore sizes. Here, we demonstrate solventassisted linker exchange (SALE) as a versatile method to prepare highly porous melt-quenched MOF glasses from the canonical ZIF-8. Two additional organic linkers are incorporated into the non-meltable ZIF-8, yielding high-entropy, linker-exchanged ZIF-8 derivatives undergoing crystal-to-liquid-to-glass phase transitions by thermal treatment. The ZIF-8 glasses demonstrate specific pore volumes of about 0.2 cm3g–1, adsorb large amounts of technologically relevant C3 and C4 hydrocarbons, and feature high kinetic sorption selectivities for the separation of propylene from propane.Item The halogen bond to ethers - prototypic molecules and experimental electron density(2024-08-05) Schmidt, Annika; Krupp, Anna; Kleinheider, Johannes; Binnenbrinkmann, Tamara M. L.; Wang, Ruimin; Englert, Ulli; Strohmann, CarstenHalogen bonds to dialkyl ether molecules have remained largely unexplored. We here address the synthesis and the structural chemistry of the first halogen-bonded noncyclic alkyl ethers, combining 1,4-diiodotetrafluorobenzene and the prototypic or commonly used ethers dimethyl ether, tetrahydrofuran, and methyl-tert-butyl ether as halogen acceptors. Two different structural motifs based on moderately strong halogen bonds were obtained: Discrete trimolecular aggregates are formed, and unexpected halogen-bonded supramolecular chain adducts feature oxygen-bifurcated halogen bonds with 1:1 donor:acceptor ratio. Both structure types may be selectively obtained even for the same ether by adjusting the stoichiometry in the crystallization experiments. The geometric features of the etheric oxygen center were found to be flexible, in contrast to the almost linear geometry about the halogen donor atom. A high-resolution X-ray diffraction experiment on the extended adduct of dimethyl ether allowed us to study the electronic details of the acceptor-bifurcated I···O···I halogen bonds. The electron density in the bond critical points and derived properties such as the Laplacian indicate essentially electrostatic interactions and explain the geometrical flexibility of ethers in halogen bonds. Our studies demonstrate the great versatility of ethers as halogen bond acceptors, that can occur in many geometrical arrangements and whose contribution to nature’s structural designs should not be underestimated.Item CycloSiFA: the next generation of silicon-based fluoride acceptors for positron emission tomography (PET)(2023-10-18) Mawick, Matthias; Jaworski, Carolin; Bittermann, Jens; Iovkova, Ljuba; Pu, Yinglan; Wängler, Carmen; Wängler, Björn; Jurkschat, Klaus; Krause, Norbert; Schirrmacher, RalfThe ring-opening Si-fluorination of a variety of azasilole derivatives cyclo-1-(iPr2Si)−4-X−C6H3−2-CH2NR (4: R=2,6-iPr2C6H3, X=H; 4 a: R=2,4,6-Me3C6H2, X=H; 9: R=2,6-iPr2C6H3, X=tBuMe2SiO; 10: R=2,6-iPr2C6H3, X=OH; 13: R=2,6-iPr2C6H3, X=HCCCH2O; 22: R=2,6-iPr2C6H3, X=tBuMe2SiCH2O) with different 19F-fluoride sources was studied, optimized and the experience gained was used in a translational approach to create a straightforward 18F-labelling protocol for the azasilole derivatives [18F]6 and [18F]14. The latter constitutes a potential clickable CycloSiFA prosthetic group which might be used in PET tracer development using Cu-catalysed triazole formation. Based on our findings, CycloSiFA has the potential to become a new entry into non-canonical labelling methodologies for radioactive PET tracer development.Item Nonstatistical assembly of multicomponent [Pd2ABCD] cages(2024-01-19) Wu, Kai; Benchimol, Elie; Baksi, Ananya; Clever, Guido H.Self-assembled hosts, inspired by biological receptors and catalysts, show potential for sustainable synthesis, energy conversion and medicine. Implementing multiple functionalities in the form of distinguishable building blocks, however, is difficult without risking narcissistic self-sorting or statistical mess. Here, we report a systematic series of integratively self-assembled heteroleptic cages in which two square-planar PdII cations are bridged by four different bis-pyridyl ligands A, B, C and D via synergistic effects to exclusively form a single isomer — the lantern-shaped cage [Pd2ABCD]. This self-sorting goal — forming just one out of 55 possible structures — is reached under full thermodynamic control and can be realized progressively (by combining progenitors such as [Pd2A2C2] with [Pd2B2D2]), directly from ligands and PdII cations, or by mixing all four corresponding homoleptic cages. The rational design of complex multicomponent assemblies that enables the incorporation of chemical moieties in a modular approach will advance their potential applications in functional nanosystems.Item Modular enhancement of circularly polarized luminescence in Pd2A2B2 heteroleptic cages(2023-02-21) Tessarolo, Jacopo; Benchimol, Elie; Jouaiti, Abdelaziz; Hosseini, Mir Wais; Clever, Guido H.Metal-mediated assembly allows us to combine an achiral emissive ligand A with different chiral ligands (such as B) in a non-statistical fashion, obtaining Pd2A2B2 heteroleptic cages showing circularly polarized luminescence (CPL). By using the ‘shape complementary assembly’ (SCA) strategy, the cages are exclusively obtained as cis-Pd2A2B2 stereoisomers, as confirmed by NMR, MS and DFT analyses. Their unique chiroptical properties derive from the synergy of all the building blocks. Ligand B imparts the chiral information of its aliphatic backbone, comprising two stereogenic sp3 carbon centres, to the overall structure, causing CD and CPL signal induction for the chromophore on ligand A. The heteroleptic cage shows CPL with a |glum| value of 2.5 × 10−3, which is 3-times higher than that for a progenitor based on aromatic helical building block H, thus opening a rational route towards optimizing the CPL properties of self-assembled nanostructures in a modular way.Item Systematic studies on heteroleptic coordination cages(2024) Ebbert, Kristina E.; Clever, Guido H.; Merten, ChristianSupramolecular coordination cages based on square-planar Pd(II) cations in combination with bis-monodentate ligands equipped with pyridine, respectively isoquinoline donor groups, form a subclass of coordination cages and assemblies that has been extensively studied. In recent years, efforts towards the development of functional coordination cages have been made, with the usual approach to achieve this goal being the incorporation of a functional backbone followed by careful choice of linker and donor-groups. Tuning the donor-groups and linkers allowed the synthesis of heteroleptic coordination cages by designing shape-complementary ligands (SCA). Herbey, this approach has been utilized to form a wide array of heteroleptic coordination assemblies and analyze them in regard to their structure, solvent susceptibility and functional group tolerance. Furthermore, ion-mobility mass spectrometry has been established as a powerful tool in the analysis of complex mixtures of up to ten structurally related supramolecules.Item Functional heteroleptic coordination cages based on a modular approach(2024) Platzek, André; Clever, Guido H.; Hiller, WolfThis work describes the rational design of a family of endohedrally functionalized heteroleptic coordination cages of the type Pd2A2B2. These were assembled out of a modular toolbox of banana shaped ligands A based on carbazole and shape complementary ligands B with different aromatic backbones and lengths. The obtained structures were characterized by NMR spectroscopy and ESI mass spectrometry as well as for some examples with X-ray diffraction in the solid state. With installing different functional groups to the free secondary amine at the carbazole moiety, namely amides and methyl substituents a variety of coordination cages with unique properties inside the cavities were formed. The coordination cages were investigated in their ability to bind hydrogen bond acceptors. Another goal of this work was the NMR spectroscopic investigation of coordination assemblies. With the help of tailor-made NMR experiments new cage compounds were characterized. The main focus was laid on DOSY NMR experiments.Item Synthese, Charakterisierung und photophysikalische Untersuchungen von Kupfer(I)-Emittern im Zusammenhang mit Exzitonenkopplung und die Synthese heteronuklearer Systeme auf Basis von Kupfer(I)- und Gruppe(IV)-Metallen(2023) Janiak, Lars Immanuel; Steffen, Andreas; Henke, SebastianDas Design molekularer Emitter auf Basis von häufig vorkommenden Metallen, wie z.B. Kupfer(I), ist eine Herausforderung der gegenwärtigen Forschung und wird in dieser Arbeit thematisiert. Lumineszente Materialien in z.B. OLEDs enthalten häufig teure Edelmetalle mit örtlich begrenztem Vorkommen, wodurch aktuell eine geopolitische Abhängigkeit entsteht und in Zukunft der Bedarf für die Massenprodukte nicht abgedeckt werden kann. Ein weiteres Problem von OLEDs ist die Stabilität und Lichtsättigung, die aufgrund niedriger strahlender Ratenkonstanten die Lebenszeit des Bauteils begrenzen. Organometallkomplexe bieten den Vorteil einer hohen Spin-Bahn-Kopplung (SOC), wodurch Singulett- mit Triplettzuständen koppeln und eine effiziente Phosphoreszenz erreichen. Nachteilig ist jedoch, dass Phosphoreszenz sich durch verhältnismäßig lange Lebenszeiten auszeichnet. Diese Problematik kann mit dem alternativen und vielversprechenden Emissionsmechanismus der thermisch aktivierten verzögerten Fluoreszenz (TADF) umgangen werden, der Zugang zu deutlich kürzeren Lebenszeiten und hohen strahlenden Ratenkonstanten 𝑘𝑟 ermöglicht. Einen weiteren Lösungs-ansatz bietet die Verwendung des physikalischen Phänomens der intramolekularen Exzitonenkopplung, welches in dieser Arbeit anhand ausgewählter Kupfer(I)-Komplexe untersucht wurde. So wurde der Einfluss eines weiteren Metallzentrums in Organometallverbindungen analysiert, um das Übergangsdipolmoment μ zu erhöhen, das ein direktes Maß für die Erlaubtheit eines Übergangs darstellt. Hierzu wurden Pyrimidin- und Benzimidazol-basierte Brückenliganden verwendet, die durch zwei bidentate Koordinationsstellen eine hohe räumliche Nähe beider Metallzentren ermöglichen. Im Rahmen dieser Arbeit wurde zudem mit S-BINAP, POP und Xantphos der Einfluss verschiedener bidentater Phosphanliganden, aber auch des N-heterocyclischen 2,4-Di-isopropylphenyl-substituierten ARDUENGO-Carbens, auf die photophysikalischen Eigenschaften im Festkörper untersucht. Insbesondere bei bpm-basierten Kupfer(I)-Komplexen wurden kürzere Lebenszeiten mit gleichbleibend niedrigen Quantenaus-beuten detektiert, während für die strahlende Ratenkonstante 𝑘𝑟 bei pmbim- und bzim-basierten Systemen keine Zunahme zu beobachten war. Des Weiteren wurden einige phosphoreszierende Blaulichtemitter auf bzim-Basis mit Quantenausbeuten von bis zu 𝛷 = 0.61 charakterisiert. Zudem wurden bpm-basierte bimetallische Komplexe mit ungewöhnlichen reversiblen Reduktionspotentialen isoliert, welche sich als potenzielle Ein-Elektronen-Transferreagenzien ausweisen. Zusätzlich wurden photokatalytische Umwandlungen mittels DEXTER-Energietransfer von bzim-basierten Kupfer(I)-Komplexen erfolgreich durchgeführt. Eine weitere Herausforderung stellt die Bildung des anti-MARKOVNIKOV-Produkts in der Hydroaminierung da. Aufgrund verschiedener thermodynamischer und kinetischer Barrieren ist das anti-MARKOVNIKOV-Produkt in der Hydroaminierung auf direktem Weg schlecht zugänglich. Gruppe(IV)-Metalle sind in der Lage diese Reaktion zu katalysieren. Aufgrund ihrer geringen Toleranz gegenüber funktionaler Gruppen und geringer Ausbeuten des anti-MAR-KOVNIKOV-Produkts jedoch limitiert. Im zweiten Teil der Arbeit wurden daher heteronukleare Systeme auf Basis von Kupfer(I)- und Gruppe(IV)-Metallen untersucht, welche in Zukunft als bimetallische Photokatalysatoren für die Hydroaminierung eingesetzt werden sollen. Priorität lag hierbei auf der Synthese und Isolation von derartigen Metallkomplexen. Während sich Gruppe(IV)-Amidokomplexe nicht für die Umsetzung mit Kupfer(I)-Komplexen eigneten, konnte durch den Wechsel auf Gruppe(IV)-Halogenidkomplexe eine erste heteronukleare Spezies auf Basis von Cu(I) und Zr(IV) nachgewiesen werden. Zudem konnten weitere neuartige Gruppe(IV)-pmbim-Verbindungen und ein trimetallischer Komplex auf Basis von einem Ti(IV)-Atom und zwei Cu(I)-Atomen isoliert werden. Letzterer zeichnet sich durch eine intensive Absorption über das gesamte sichtbare Spektrum aus.Item Tuning the high-pressure phase behaviour of highly compressible zeolitic imidazolate frameworks: from discontinuous to continuous pore closure by linker substitution(2022-02-04) Song, Jianbo; Pallach, Roman; Frentzel-Beyme, Louis; Kolodzeiski, Pascal; Kieslich, Gregor; Vervoorts, Pia; Hobday, Claire L.; Henke, SebastianThe high-pressure behaviour of flexible zeolitic imidazolate frameworks (ZIFs) of the ZIF-62 family with the chemical composition M(im)2−x(bim)x is presented (M2+=Zn2+, Co2+; im−=imidazolate; bim−=benzimidazolate, 0.02≤x≤0.37). High-pressure powder X-ray diffraction shows that the materials contract reversibly from an open pore (op) to a closed pore (cp) phase under a hydrostatic pressure of up to 4000 bar. Sequentially increasing the bim− fraction (x) reinforces the framework, leading to an increased threshold pressure for the op-to-cp phase transition, while the total volume contraction across the transition decreases. Most importantly, the typical discontinuous op-to-cp transition (first order) changes to an unusual continuous transition (second order) for x≥0.35. This allows finetuning of the void volume and the pore size of the material continuously by adjusting the pressure, thus opening new possibilities for MOFs in pressure-switchable devices, membranes, and actuators.Item Synthese und Studien photoaktiver Übergangsmetallkomplexe(2023) Koop, Stefan; Steffen, Andreas; Henke, SebastianDer Fokus dieser Dissertation lag in der Synthese und Untersuchung photoaktiver Übergangsmetallkomplexe. Im ersten Projekt wurde die Darstellung neuartiger NHC-Übergangsmetallkomplexe auf Basis von Mangan und Vanadium und ihre Eignung als photoinduzierte, schaltbare Radikalspezies untersucht. Neben dieser wurde im zweiten Projekt die Synthese bimetallischer Photokatalysatoren auf Basis von Kupfer und Rhodium/Iridium und deren Eignung für Hydroaminierungsreaktionen untersucht. Es gelang der Einblick in die Synthese und Darstellung vier neuartiger bimetallischer Komplexe. Im letzten Projekt dieser Promotionsarbeit wurde die Synthese und Untersuchung von photolumineszenten Zn(II)-Komplexen in niedrigen Koordinationsmodi, welche Carbenliganden als π-Chromophore tragen. Neben der erfolgreichen Synthese trigonaler Zn(II)-Komplexe, konnte ein Einblick in deren photophysikalischen Verhaltensweisen gewonnen werden. Diese Ergebnisse liefern eine neue Klasse von seltenen phosphoreszierenden Zn(II)-Komplexen, die für photokatalytische Anwendungen interessant sein könnten.Item Breathing porous liquids based on responsive metal-organic framework particles(2023-07-14) Koutsianos, Athanasios; Pallach, Roman; Frentzel-Beyme, Louis; Das, Chinmoy; Paulus, Michael; Sternemann, Christian; Henke, SebastianResponsive metal-organic frameworks (MOFs) that display sigmoidal gas sorption isotherms triggered by discrete gas pressure-induced structural transformations are highly promising materials for energy related applications. However, their lack of transportability via continuous flow hinders their application in systems and designs that rely on liquid agents. We herein present examples of responsive liquid systems which exhibit a breathing behaviour and show step-shaped gas sorption isotherms, akin to the distinct oxygen saturation curve of haemoglobin in blood. Dispersions of flexible MOF nanocrystals in a size-excluded silicone oil form stable porous liquids exhibiting gated uptake for CO2, propane and propylene, as characterized by sigmoidal gas sorption isotherms with distinct transition steps. In situ X-ray diffraction studies show that the sigmoidal gas sorption curve is caused by a narrow pore to large pore phase transformation of the flexible MOF nanocrystals, which respond to gas pressure despite being dispersed in silicone oil. Given the established flexible nature and tunability of a range of MOFs, these results herald the advent of breathing porous liquids whose sorption properties can be tuned rationally for a variety of technological applications.Item Ultra‐long lived luminescent triplet excited states in cyclic (alkyl)(amino)carbene complexes of Zn(II) halides(2022-05-18) Mrózek, Ondřej; Gernert, Markus; Belyaev, Andrey; Mitra, Mousree; Janiak, Lars; Marian, Christel M.; Steffen, AndreasThe high element abundance and d10 electron configuration make ZnII-based compounds attractive candidates for the development of novel photoactive molecules. Although a large library of purely fluorescent compounds exists, emission involving triplet excited states is a rare phenomenon for zinc complexes. We have investigated the photophysical and -chemical properties of a series of dimeric and monomeric ZnII halide complexes bearing a cyclic (alkyl)(amino)carbene (cAAC) as chromophore unit. Specifically, [(cAAC)XZn(μ-X)2ZnX(cAAC)] (X=Cl (1), Br (2), I (3)) and [ZnX2(cAAC)(NCMe)] (X=Br (4), I (5)) were isolated and fully characterized, showing intense visible light photoluminescence under UV irradiation at 297 K and fast photo-induced transformation. At 77 K, the compounds exhibit improved stability allowing to record ultra-long lifetimes in the millisecond regime. DFT/MRCI calculations confirm that the emission stems from 3XCT/LEcAAC states and indicate the phototransformation to be related to asymmetric distortion of the complexes by cAAC ligand rotation. This study enhances our understanding of the excited state properties for future development and application of new classes of ZnII phosphorescent complexes.