ABSTRACT
Two N-alkyloxy-N'-phenylimidazolium proligands and the corresponding platinum(II) cyclometalated N-alkyloxyimidazol-2-ylidene complexes with ß-diketonate auxiliary ligands, [(CNOHC^C*)Pt(Lâ©L)] (Lâ©L = acetyacetonate (acac) or 1,3-bis(2,4,6-trimethylphenyl)-propane-1,3-dionato (mesacac)) were synthesized and fully characterized. In addition, a Au(I) monocarbene complex was synthesized, isolated and characterized. Solid-state structures of two cyclometalated platinum(II) NOHC complexes and the Au(I) NOHC complex were obtained providing structural proof.
ABSTRACT
A novel class of cyclometalated platinum(II) complexes-previously considered to be inaccessible-was synthesized by an improved synthetic route utilizing ligands predicted by density functional theory calculations. Based on a concise quantum chemical screening three model ligands with varying steric demand were chosen and a series of six photoluminescent C^C* cyclometalated platinum(II) formamidinate complexes was obtained. The least sterically demanding ligand led to a bimetallic complex in two isomeric forms, which could be separated and confirmed by the corresponding solid-state structures. Sterically more hindered amidinate ligands gave the monometallic complexes supporting the theoretical predictions. The monometallic complexes show a significant hypsochromic shift of the emission wavelength, explained by the loss of the metal-metal interactions. Depending on the cyclometalating ligand quantum yields up to 87 % with short decay times were found for this new class of phosphorescent green-blue to pure blue platinum(II) emitters.
ABSTRACT
Chemiophoretic nano- and micromotors require a constant flow of product molecules to maintain a gradient that enables their propulsion. Apart from a smaller number of redox reactions that have been used, catalytic reactions are the main source of energy with the obvious benefit of making on-board fuel storage obsolete. However, the decomposition of H2O2 seems to strongly dominate the literature and although motion in H2O through water splitting is becoming more popular, so far only a few different reactions have been used for propulsion of photocatalytic microswimmers. Here, we investigate the possibility of extending the range of possible fuelling reactions to organic reactions with high significance in organic synthesis - the oxidation of amines to imines. Herein, motion of the microswimmers is analysed at different amine concentrations and light intensities. The findings thereof are correlated with the reaction products identified and quantified by gas chromatography (GC).
