Ryberg Klausen (clavetuba2)

A first coordination [2.2.2]cryptand(K+)2FeII(TI˙-)(TI2-)2·2C6H4Cl2 (1) complex of iron(ii) containing radical anions and dianions of thioindigo (TI) was obtained. The complex has two high-spin FeII centers bound by two oxygen atoms, and the TI˙- radical anions are coordinated to each FeII. As a result, the 4-spin system consisting of TI˙- (S = 1/2)-FeII (S = 2)-FeII (S = 2)-TI˙- (S = 1/2) coupled spins is formed within a dimer with strong FeII-FeII (J = -51.1 cm-1) and weaker FeII-TI˙- interactions of (J = -35.4 cm-1).We describe the functionalisation of the previously reported uranium(iii) β-diketiminate complex (BDI)UI2(THF)2 (1) with one and two equivalents of a sterically demanding 2,6-diisopropylphenolate ligand (ODipp) leading to the formation of two heteroleptic complexes [(BDI)UI(ODipp)]2 (2) and (BDI)U(ODipp)2 (3). The latter is a rare example of a tetrahedral uranium(iii) complex, and it shows single-molecule magnet behaviour.Surface modification effects of graphite and organic solvents on Ti were investigated by thermogravimetry (TG), Raman spectroscopy, and transmission electron microscopy (TEM) observations to improve its hydrogen absorption properties. As a result, Ti ball-milled with graphite showed high reactivity and selectivity for hydrogen with high durability.A 3D-printed microfluidic fuel cell is presented. Fused deposition modeling is used to build a microchannel with a 0.015 cm2 cross-sectional area for stable colaminar flow conditions. A new 3D-Printed cell fed by glycerol displays a power density of 175 mW cm-2 at 0.9 V and 1.8 V of open-circuit voltage.Four heteroleptic Ir(iii) complexes (Ir-1-Ir-4) with varied π-conjugated diimine ligands were synthesized. Their optical properties were investigated systematically via spectroscopic methods, in order to elucidate the influence of the extended π-conjugation on the singlet and triplet states of the molecules. All these Ir(iii) complexes exhibit ligand localized 1π,π* transitions below 370 nm, and broad metal-to-ligand and ligand-to-ligand charge transfer (MLCT/LLCT) absorption bands in the visible region. Extending the π-conjugation in diimine ligands influences the electron distribution of the triplet state. The 3π,π* dominated Ir(iii) complexes (Ir-3 and Ir-4) exhibit long-lived triplet states and low phosphorescence quantum yields, compared with the charge transfer dominated Ir(iii) complexes (Ir-1 and Ir-2). Complexes Ir-3 and Ir-4 exhibit broadband transient absorption spectra from 420 to 750 nm, between which the nonlinear absorption could be observed by virtue of reverse saturable absorption. The results of nonlinear transmission measurements using 532 nm laser pulses further elucidate that selected complexes Ir-3 and Ir-4 are promising candidates for optical limiting applications.This work shows that highly uniform worm micelles formed by polymerisation induced self-assembly can be obtained via simple post-synthesis sonication. Importantly, this straightforward and versatile strategy yields exceptionally monodisperse worms with tunable aspect ratios ranging from 7.2 to 17.6 by simply changing the sonication time.We report multi-modal-control over the assembly behaviour of a first-generation molecular motor bola-amphiphile in water by light, pH and the choice of counter-ions. These findings open up opportunities for the development of materials that reconfigurate enabling complex functions in response to different stimuli.The high yielding CuI-mediated click reaction is an effective procedure for the preparation of oligoporphyrinoid conjugates. However, the CuI catalyst leads to the adventitious and usually undesirable insertion of Cu ions into any non-metalated porphyrinoid centers during reaction. Here we report a "sacrificial rotaxane" strategy for the multifunctionalization of porphyrins with free base corroles without incidental copper insertion. This strategy can be considered a general method for implementing CuI-mediated click reactions