Getting the green light! Substituted arylazopyrazoles (AAPs) have been investigated as supramolecular photoswitches in aqueous solution. Selective photostationary states (PSSs) and improved binding affinities to β-cyclodextrin have been determined. The experimental findings are supported by results from DFT calculations.
Versatile photoresponsive gels based on tripodal low molecular weight gelators (LMWGs) are reported. A cyclohexane‐1,3,5‐tricarboxamide (CTA) core provides face‐to‐face hydrogen bonding and a planar conformation, inducing the self‐assembly of supramolecular polymers. The CTA core was substituted with three arylazopyrazole (AAP) arms. AAP is a molecular photoswitch that isomerizes reversibly under alternating UV and green light irradiation. The E isomer of AAP is planar, favoring the self‐assembly, whereas the Z isomer has a twisted structure, leading to a disassembly of the supramolecular polymers. By using tailor‐made molecular design of the tripodal gelator, light‐responsive organogels and hydrogels were obtained. Additionally, in the case of the hydrogels, AAP was coupled to the core through hydrazones, so that the hydrogelator and, hence, the photoresponsive hydrogel could also be assembled and disassembled by using dynamic covalent chemistry.
In this work, we describe the synthesis as well as structural, photophysical, and theoretical investigation of a new coordination chemical concept involving rhenium(I) complexes bearing monoanionic 1,2,4-triazolylpyridine-based bidentate chromophores. The X-ray diffractometric analysis of single crystals revealed particular packing features: the trifluoromethylated exemplar displayed two kinds of arrangements of the coordination centers, where the bidentate ligands at the edges of the unit cell are staggered parallel to each other, whereas those inside show antiparallel stacking with respect to the external ligands. On the other hand, the complexes bearing an adamantyl substituent yield a linear arrangement, where the bulky moiety of one luminophore points to the pyridine center of the adjacent ligand of the neighboring complex while including methanol molecules hydrogen-bonded to the triazolato unit. We observed that the photophysical properties of the complexes (photoexcited-state lifetimes, photoluminescence maxima and quantum yields) can be adjusted by tuning of the substitution pattern at the bidentate luminophore as well as by variation of the monodentate coligand. The photoluminescence spectra and photoexcited-state lifetimes of the crystalline phases were measured by phosphorescence lifetime micro(spectro)scopy. Interestingly, the vibrationally resolved emission spectra of the crystals closely resemble those of diluted frozen glassy matrixes at 77 K, in contrast with the broad bands observed in amorphous solids and in fluid solutions, where the charge-transfer character is enhanced. While the photoluminescence quantum yields (ΦL) reach up to 15%, the complexes are able to attain up to 55% efficiency regarding the photosensitization of 1O2 (ΦΔ), depending on the combination of luminophore and coligand. Theoretical calculations showed that the photoexcited triplet (T1) state has a metal–ligand-to-ligand charge-transfer character, where promotion to the excited electronic configuration shortens the Re(I)–N bond involving the bidentate triazolylpyridine while stretching the three fac-CO–Re(I) bonds as well as the linkage to the axial monodentate coligand. The calculated vertical (E vl) and 0–0 (E (0–0)) radiative transition energies are in very good agreement with the experimental values (E exp lum).
In this work, the synthesis, structural and photophysical characterization of six phosphorescent H 2 O-soluble Pt(II) complexes are reported while addressing their emission maxima, photoluminescence quantum yields (Φ L ), lifetimes (τ), aggregation tendency, and microenvironment sensitivity as a function of the substitution pattern on the main tridentate luminophore. Different ancillary ligands, namely, a trisulfonated phosphane and maltohexaose-conjugated pyridines (with or without amide bridges), were introduced and evaluated for the realization of switch-on-photoluminescent labels reporting on the microenvironment sensed in biofilms of Gram + and Gram − models, namely, Staphylococcus aureus and Escherichia coli. With the aid of confocal luminescence micro(spectro)scopy, we observed that selected complexes specifically interact with the biofilms while leaving planktonic cells unlabeled. By using photoluminescence lifetime imaging microscopy, excited-state lifetimes within S. aureus biofilms were measured. The photoluminescence intensities were drastically boosted, and the excited state lifetimes were significantly prolonged upon binding to the viscous biofilm matrix, mainly due to the suppression of radiationless deactivation pathways upon shielding from physical quenching processes, such as interactions with solvent molecules and 3 O 2 . The best performances were attained for non-aggregating complexes with maltohexaose targeting units and without amide bridges. Notably, in the absence of the maltodextrin, a hydrophobic adamantyl moiety suffices to attain a sizeable labeling capacity. Moreover, photoluminescence studies showed that selected complexes can also effectively interact with E. coli biofilms, where the bacterial cells are able to partially uptake the maltodextrin-based agents. In summary, the herein introduced concepts enable the development of specific biofilm reporters providing spatial resolution as well as lifetime-and spectrum-based readouts. Considering that most theragnostic agents reported so far mainly address metabolically active bacteria at the surface of biofilms but without reaching cells deeply immersed in the matrix, a new platform with a clear structure-property correlation is provided for the early detection of such bacterial arrays.
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