In situ Cyclization of Aromatic Thioethers in Emissive Materials to Generate Phosphorescent Dibenzothiophenes.

In this contribution, we explored the photocyclization of thioethers to highly substituted dibenzothiophenes (DBT) using solely UV-light without any need for additives. This cost-effective, robust and environmentally friendly approach yielded phosphorescent compounds, which were characterized through X-ray crystallography and state-of-the-art photophysical methods. The resulting DBTs feature ultralong photoluminescence lifetimes and quantum yields close to unity in frozen glassy matrices. The reaction mechanism was investigated in detail through a combination of quantum chemical calculations and experimental results, providing evidence that triplet states are involved in the cyclization process. Additionally, the photoreaction can also be induced within materials. For this purpose, the precursors can be integrated into polymer films or polymer resins suitable for 3D printing. Irradiation of these polymeric objects allows motifs with ultralong phosphorescence to be irreversibly inscribed through the proceeding photocyclization. The in situ photogeneration of DBTs from aromatic thioethers overcomes the observed incompatibilities regarding solubility in polymer resins for 3D printing.

Catalytic hydroboration of aldehydes and ketones with an electron-rich acyclic metallasilylene.

The application of main group metal complexes in catalytic reactions is of increasing interest. Here we show that the electron-rich, acyclic metallasilylene L'(Cl)GaSiL C (L' = HC[C(Me)NDipp]2, Dipp = 2,6-iPr2C6H3; L = PhC(NtBu)2) acts as a precatalyst in the hydroboration of aldehydes with HBPin. Mechanistic studies with iso-valeraldehyde show that silylene C first reacts with the aldehyde with [2 + 1] cycloaddition in an oxidative addition to the oxasilirane 1, followed by formation of the alkoxysilylene LSiOCH[Ga(Cl)L']CH2CHMe2 (2), whose formation formally results from a reductive elimination reaction at the Si center. Alkoxysilylene 2 represents the active hydroboration catalyst and shows the highest catalytic activity with n-hexanal (reaction time: 40 min, yield: >99%, TOF = 150 h-1) at room temperature with a catalytic load of only 1 mol%. Furthermore, the hydroboration reaction catalysed by alkoxysilylene 2 is a living reaction with good chemoselectivity. Quantum chemical calculations not only provide mechanistic insights into the formation of alkoxysilylene 2 but also show that two completely different hydroboration mechanisms are possible.

From Neutral Diarsenes to Diarsene Radical Ions and Diarsene Dications.

Diarsene [L(MeO)GaAs]2 (L=HC[C(Me)N(Ar)]2, Ar=2,6-iPr2C6H3, 4) reacts with MeOTf and MeNHC (MeNHC=1,3,4,5-tetra-methylimidazol-2-ylidene) to the diarsene [L(TfO)GaAs]2 (5) and the carbene-coordinated diarsene [L(MeO)GaAsAs(MeNHC)Ga(OMe)L] (6). The NHC-coordination results in an inversion of the redox properties of the diarsene 4, which shows only a reversible reduction event at E1/2=-2.06 V vs Fc0/+1, whereas the carbene-coordinated diarsene 6 shows a reversible oxidation event at E1/2=-1.31 V vs Fc0/+1. Single electron transfer reactions of 4 and 6 yielded [K[2.2.2.]cryp][L(MeO)GaAs]2 (8) and [L(MeO)GaAsAs(MeNHC)-Ga(OMe)L][B(C6F5)4] (9) containing the radical anion [L(MeO)GaAs]2⋅- (8⋅-) and the NHC-coordinated radical cation [L(MeO)GaAsAs(MeNHC)Ga(OMe)L]⋅+ (9⋅+), respectively, while the salt-elimination reaction of the triflate-coordinated diarsene 5 with Na[B(C6F5)4] gave [LGaAs]2[B(C6F5)4]2 (11) containing the dication [LGaAs]2 2+ (112+). Compounds 1-11 were characterized by 1H and 13C NMR, EPR (8, 9), IR, and UV-Vis spectroscopy and by single crystal X-ray diffraction (sc-XRD). DFT calculations provided a detailed understanding of the electronic nature of the diarsenes (4, 6) and the radical ions (8⋅-, 9⋅+), respectively.

The Origin of Dual-Emission in PLICT Compounds - an Empirical Approach.

Fluorescence spectroscopy proves to be a powerful and versatile tool in scientific research, demanding ongoing advancements of fluorescence probes to cater to a broad range of applications. The particular interest lies in the development of fluorophores with multiplexing capability, emitting from more than one excited state depending on the polarity and viscosity of the surrounding medium. Here, we present a variety of novel dual planarized intramolecular charge transfer (PLICT) emitters based on cyano-1-aminoindole structures. We have chosen a combination of experimental studies, theoretical calculations and the creation of a unique fluorophore cataloging map. This map serves as a useful tool for empirically determining the origin of both fluorescence bands.

Multiple ethylene activation by heteroleptic L(Cl)Ga-substituted germylenes.

Ethylene insertion into the Ga-Ge bond of the L(Cl)Ga-substituted germylene LGa(µ-Cl)GeDMP 1 (L = HC(C(Me)NAr)2, Ar = 2,6-iPr2C6H3; DMP = 2,6-Mes2C6H3, Mes = 2,4,6-Me3C6H2) at ambient temperature is followed by dimerization of the as-formed germylene to give the digermene 3, which further reacted with ethylene in a [2 + 2] cycloaddition to give the 1,2-digermacyclobutane 4. In marked contrast, the amino-substituted germylene L(Cl)GaGeN(SiMe3)Ar 2 reacted directly to the 1,2-digermacyclobutane 5. Quantum chemical calculations confirmed the assumed reaction mechanism, hence demonstrating the crucial role of the substituent on the reaction mechanism.

Measurement of Nanometer Distances in Solution via 13 C NMR Spectroscopy-Shrinking of Macrocycles with Increasing Temperature.

For a molecular system, size and shape are of elementary importance for its function and properties. Therefore, the determination of distances within a molecule is essential. However, the commonly used methods are only suitable for distances smaller than 4 Šor larger than 15 Å. Here, we show that by incorporating a molecular spring, we can measure distances in macrocycles in the range of 10 Šusing 13 C NMR spectroscopy. The accuracy of the method also allows to determine the temperature dependence of the distances. In one case, we find a contraction of the length by almost 10 % upon heating. This shrinking due to heating can be considered as inverse thermoelasticity at the molecular level and is a previously completely overlooked phenomenon that can be used in the future as a tool to change the length and, thus, the function of a system.