Ring Opening Reactions of β‐Propiolactam in Superacidic Media

The reaction of β-propiolactam in the superacidic systems HF/MF5 (M=Sb, As) led to the formation of monoprotonated 3-aminopropanoyl fluoride in the form of [C(O)F(CH2)2NH3][SbF6] and [C(O)F(CH2)2NH3][AsF6]. In the presence of traces of water, the diprotonated species β-alanine [C(OH)2(CH2)2NH3][AsF6]2 was synthesized for the first time. All salts were characterized by low-temperature infrared and Raman spectroscopy. Additionally, single-crystal X-ray analyses were conducted in the case of [C(O)F(CH2)2NH3][SbF6] and [C(OH)2(CH2)2NH3][AsF6]2. By using SO2 instead of HF as the solvent, the salt [C(OH)2(CH2)2NHSO][SbF6]2 was obtained, and single-crystal X-ray analysis of this salt containing a thionylimide moiety was conducted. For the formation of these open-chain compounds, an acyl cationic species as intermediate is assumed, which is formed from N-protonated β-propiolactam. Quantum chemical calculations at the B3LYP/aug-cc-pVTZ and MP2/aug-cc-pVTZ levels of theory were carried out to gain a better understanding of the formation and the structural properties of protonated β-propiolactam

A DNA‐Stabilized Ag₁₈¹²+ Cluster with Excitation‐Intensity‐Dependent Dual Emission

DNA-stabilized silver nanoclusters (DNA-AgNCs) are easily tunable emitters with intriguing photophysical properties. Here, a DNA-AgNC with dual emission in the red and near-infrared (NIR) regions is presented. Mass spectrometry data showed that two DNA strands stabilize 18 silver atoms with a nanocluster charge of 12+. Besides determining the composition and charge of DNA2[Ag18]12+, steady-state and time-resolved methods were applied to characterize the picosecond red fluorescence and the relatively intense microsecond-lived NIR luminescence. During this process, the luminescence-to-fluorescence ratio was found to be excitation-intensity-dependent. This peculiar feature is very rare for molecular emitters and allows the use of DNA2[Ag18]12+ as a nanoscale excitation intensity probe. For this purpose, calibration curves were constructed using three different approaches based either on steady-state or time-resolved emission measurements. The results showed that processes like thermally activated delayed fluorescence (TADF) or photon upconversion through triplet-triplet annihilation (TTA) could be excluded for DNA2[Ag18]12+. We, therefore, speculate that the ratiometric excitation intensity response could be the result of optically activated delayed fluorescence

DNA Stabilizes Eight-Electron Superatom Silver Nanoclusters with Broadband Downconversion and Microsecond-Lived Luminescence.

DNA oligomers are known to serve as stabilizing ligands for silver nanoclusters (AgN-DNAs) with rod-like nanocluster geometries and nanosecond-lived fluorescence. Here, we report two AgN-DNAs that possess distinctly different structural properties and are the first to exhibit only microsecond-lived luminescence. These emitters are characterized by significant broadband downconversion from the ultraviolet/visible to the near-infrared region. Circular dichroism spectroscopy shows that the structures of these two AgN-DNAs differ significantly from previously reported AgN-DNAs. We find that these nanoclusters contain eight valence electrons, making them the first reported DNA-stabilized luminescent quasi-spherical superatoms. This work demonstrates the important role that nanocluster composition and geometry play in dictating luminescence properties of AgN-DNAs and significantly expands the space of structure-property relations that can be achieved for AgN-DNAs