The recently reported luminescent chromium(III) complex 1 ([Cr(ddpd) ] ; ddpd=N,N'-dimethyl-N,N'-dipyridine-2-yl-pyridine-2,6-diamine) shows exceptionally strong near-IR emission at 775 nm in water under ambient conditions (Φ=11 %) with a microsecond lifetime as the ligand design in 1 effectively eliminates non-radiative decay pathways, such as photosubstitution, back-intersystem crossing, and trigonal twists. In the absence of energy acceptors, such as dioxygen, the remaining decay pathways are energy transfer to high energy solvent and ligand oscillators, namely OH and CH stretching vibrations. Selective deuteration of the solvents and the ddpd ligands probes the efficiency of these oscillators in the excited state deactivation. Addressing these energy-transfer pathways in the first and second coordination sphere furnishes a record 30 % quantum yield and a 2.3 millisecond lifetime for a metal complex with an earth-abundant metal ion in solution at room temperature.

Der kürzlich publizierte Chrom(III)‐Komplex 13+ ([Cr(ddpd)2]3+) zeigt in wässriger Lösung unter Umgebungsbedingungen eine bemerkenswert starke Emission im nahen Infrarot‐Bereich mit einer Emissionswellenlänge von 775 nm. Geschicktes Ligandendesign verhindert strahlungslose Desaktivierungsprozesse wie Photosubstitution, Rück‐Intersystem‐Crossing und trigonale Verzerrungen und führt damit zu einer Phosphoreszenzlebensdauer im Bereich von Mikrosekunden. In Abwesenheit von Energieakzeptoren wie molekularem Sauerstoff verbleibt nur Energietransfer zu hochenergetischen Oszillatoren der Liganden und Lösungsmittelmoleküle wie beispielsweise OH‐ und CH‐Streckschwingungen als Desaktivierungspfad. Selektive Deuterierung der ddpd‐Liganden und der Lösungsmittel lässt die Effizienz dieser Oszillatoren bei der Desaktivierung angeregter Zustände erkennbar werden. Gezieltes Ausschalten dieser Relaxationspfade führt zu einer Quantenausbeute von 30 % und einer Lebensdauer von 2.3 Millisekunden bei Raumtemperatur in Lösung – Rekordwerte für einen Komplex, der auf dem Element Chrom basiert. Diese fundamentalen Erkenntnisse ebnen den Weg für gezieltes Ligandendesign zur Synthese lumineszierender Komplexe mit gut verfügbaren Übergangsmetallen.

A general and efficient Ni-catalyzed coupling of challenging aryl chlorides and in situ generated aliphatic and aromatic thiolates is described. The employed oncycle, air-stable defined Ni precatalysts allow for transformation of a broad scope of substrates. A variety of functional groups and heterocyclic motifs as well as structurally varied thiols are tolerated at unprecedented moderate catalyst loadings and reaction temperatures. Depending on reaction conditions, aryl thiols can selectively undergo

For investigations on the biological functions of oligosaccharides and peptidomimetics, new asparagine-based mono- and disaccharides containing glycopeptides were prepared in solution. The applicability of two common peptide coupling reagents, using an orthogonal Fmoc/t-Bu strategy along with acetyl protecting groups for the carbohydrate moiety, was studied. Thus, the prepared libraries of glycopeptides were designed as model systems of cell surfaces for future investigations by combined preparative mass spectroscopy and scanning tunneling microscopy (STM) using soft-landing electrospray beam deposition (ES-IBD), on metal surfaces.

Besides the most common sequon of amino acids found in glycopeptides, namely, N-X-S/T, where X can be any amino acid except proline, a small number of nonconsensus motifs have been found in both eukaryotic and prokaryotic organisms, for example, Q-G-T. Because of the importance of glycopeptides in biotechnology and pharmacy, an adequate synthetic approach to these structures is highly important. In this manuscript, we report the efficient chemical batch synthesis of new glutamine-based glycopeptide structures, which can be used to represent cell surface elements in further biological investigations.