Highly emissive 4-carbazole-appended salen-indium complex: the effect of strong donor-acceptor interaction.

Herein, we report our findings on 4-carbazole (CBZ)-appended salen-based indium complexes, CBZIn1 and CBZIn2, which feature diimine bridges exhibiting different electron-accepting properties. Notably, CBZIn2 exhibited a significantly higher photoluminescence quantum efficiency (PLQY, ΦPL) in toluene than CBZIn1, with a value over 15 times greater (ΦPL = 57.7% for CBZIn2; ΦPL = 3.7% for CBZIn1). In particular, in the rigid state of THF at 77 K, CBZIn2 exhibited a near-unity PLQY of 98.2%. Even in the PMMA film, CBZIn2 maintained a high level of PLQY (ΦPL = 70.2%). These results can be attributed to the highly efficient radiative decay process based on intramolecular charge-transfer (ICT) transition between the moderately twisted CBZ, characterized by its conformational rigidity and the 1,2-dicyanoethylene-bridged salen, which exhibits a strong electron-accepting ability. Furthermore, these findings are supported by theoretical calculations.

Unlocking Cu(I)-Mediated Catalytic Pathways for Efficient ROS Generation by Incorporating an Oxazole-Based Histidine Surrogate into Cu(II)-ATCUN Complexes.

The catalytic redox activity of Cu(II) bound to the amino-terminal copper and nickel (ATCUN) binding motif (Xxx-Zzz-His, XZH) is stimulating the development of catalytic metallodrugs based on reactive oxygen species (ROS)-mediated biomolecule oxidation. However, low Cu(I) availability resulting from the strong Cu(II) binding affinity of the ATCUN motif is regarded as a limitation to efficient ROS generation. To address this, we replaced the imidazole moiety (pKa 7.0) of Gly-Gly-His-NH2 (GGHa, a canonical ATCUN peptide) with thiazole (pKa 2.7) and oxazole (pKa 0.8), yielding GGThia and GGOxa, respectively. A newly synthesized amino acid, Fmoc-3-(4-oxazolyl)-l-alanine, served as a histidine surrogate featuring an azole ring with the lowest pKa among known analogues. Despite similar square-planar Cu(II)-N4 geometries being observed for the three Cu(II)-ATCUN complexes by electron paramagnetic resonance spectroscopy and X-ray crystallography, the azole modification enabled the Cu(II)-ATCUN complexes to exhibit significant rate enhancement for ROS-mediated DNA cleavage. Further analyses based on Cu(I)/Cu(II) binding affinities, electrochemical measurements, density functional theory calculations, and X-ray absorption spectroscopy indicated that the azole modification enhanced the accessibility of the Cu(I) oxidation state during ROS generation. Our oxazole/thiazole-containing ATCUN motifs provide a new design strategy for peptide ligands with modulated N donor ability, with potential applications in the development of ROS-mediated metallodrugs.

Crystal structure, Hirshfeld surface and photo-physical analysis of 2-nitro-3-phenyl-9H-carbazole.

The title compound, C18H12N2O2, was synthesized from a di-nitro-biphenyl-benzene derivative using a novel modification of the Cadogan reaction. The reaction has several possible ring-closed products and the title compound was separated as the major product. The X-ray crystallographic study revealed that the carbazole compound crystallizes in the monoclinic P space group and possesses a single closed Cadogan ring. There are two independent mol-ecules in the asymmetric unit. In the crystal, the mol-ecules are linked by N-H⋯O hydrogen bonding.