Norbornadiene-Quadricyclane Photoswitches with Enhanced Solar Spectrum Match.

Herein, we report monomeric and dimeric norbornadiene-quadricyclane molecular photoswitch systems intended for molecular solar thermal applications. A series of six new norbornadiene derivatives conjugated with benzothiadiazole as the acceptor unit and dithiafulvene as the donor unit were synthesized and fully characterized. The photoswitches were evaluated by experimentally and theoretically measuring optical absorption profiles and thermal conversion of quadricyclane to norbornadiene. Computational insight by density functional theory calculations at the M06-2X/def2-SVPD level of theory provided geometries, storage energies, UV-vis absorption spectra and HOMO-LUMO levels, that are used to describe the function of the molecular systems. The studied molecules exhibit absorption onset ranging from 416 nm to 595 nm due to a systemic change in their donor-acceptor character. This approach was advantageous due to the introduction of benzothiadiazole and the dimeric nature of molecular structures. The best-performing system has a half-life of 3 days.

Pyrene Functionalized Norbornadiene-Quadricyclane Fluorescent Photoswitches: Characterization of their Spectral Properties and Application in Imaging of Amyloid Beta Plaques.

This study presents the synthesis and characterization of two fluorescent norbornadiene (NBD) photoswitches, each incorporating two conjugated pyrene units. Expanding on the limited repertoire of reported photoswitchable fluorescent NBDs, we explore their properties with a focus on applications in bioimaging of amyloid beta (Aß) plaques. While the fluorescence emission of the NBD decreases upon photoisomerization, aligning with what has been previously reported, for the first time we observed luminescence after irradiation of the quadricyclane (QC) isomer. We deduce how the observed emission is induced by photoisomerization to the excited state of the parent isomer (NBD) which is then the emitting species. Thorough characterizations including NMR, UV-Vis, fluorescence, X-ray structural analysis and density functional theory (DFT) calculations provide a comprehensive understanding of these systems. Notably, one NBD-QC system exhibits exceptional durability. Additionally, these molecules serve as effective fluorescent stains targeting Aß plaques in situ, with observed NBD/QC switching within the plaques. Molecular docking simulations explore NBD interactions with amyloid, unveiling novel binding modes. These insights mark a crucial advancement in the comprehension and design of future photochromic NBDs for bioimaging applications and beyond, emphasizing their potential in studying and addressing protein aggregates.

Synthesis and Characterization of Carbon-Based Heterogeneous Catalysts for Energy Release of Molecular Solar Thermal Energy Storage Materials.

Molecular solar thermal energy storage (MOST) systems are rapidly becoming a feasible alternative to energy storage and net-zero carbon emission heating. MOST systems involve a single photoisomerization pair that incorporates light absorption, storage, and heat release processes in one recurring cycle. Despite significant recent advancements in the field, the catalytic back-reaction from MOST systems remains relatively unexplored. A wide range of applications is possible, contingent on the energy densities of the specific photoisomers. Here, we report platinum-, copper-, and nickel-based heterogeneous catalysts screened in batch conditions for the back-conversion reaction on the cyano-3-(4-methoxyphenyl)-norbornadiene/quadricyclane pair. Catalyst reactivities are investigated using structural characterization, imaging techniques, and spectroscopic analysis. Finally, the thermal stability is also explored for our best-performing catalysts.

Synthesis of Dioxa-1,7-naphthicorrole and Its Oxidized Porphyrinoid as a Potential Built-In Linker for Biomolecules.

The first aromatic benzicorrole termed naphthicorrole was synthesized with a carbon donor containing more than six members. Its oxidized (enedione-embedded) porphyrinoid was also obtained using different meso-aryl substitutions under sequential oxidation conditions. The resulting enedione motif of the nonaromatic porphyrinoid was regioselective to the C2 position for S or N nucleophiles. Thus, the oxidized porphyrinoid was tested as a built-in linker for biomolecules. The progress of the reaction was visually monitored due to their different conjugation pathways.

o-(2-Thienyl)vinylarene as an Alternative Synthetic Motif for Porphyrinoids: o-Arene-Connected Porphyrinoids.

o-Arene-connected porphyrinoids were synthesized with o-(2-thienyl)vinylarene motif as a new building block for porphyrinoids. This motif can replace meso-aryl-substituted dipyrromethene and serve as a command key arranging o-connectivity of porphyrinoid. While 6a (benzene version) is very weak, 6b (pyridine version) shows a substantial amount of diatropic ring current due to reduced steric hindrance (without H23) and rigidified Pd-6a became more aromatic than 6b.

Carbaporphyrin Dimers That Bear a Rigid Naphthalene Motif as an Internal Strap.

The first fully connected aromatic carbaporphyrin dimer (6) and its bis-Pd complex (6-Pd2) that bear a rigid naphthalene motif as an internal strap were synthesized. These dimers consisted of two aromatic carbaporphyrins that shared a naphthalene motif. The π-electron conjugation of the obtained macrocycles was proposed to have two separated local 22 π-electron pathways and a 34 π-electron pathway. Their weak aromaticity was fully supported by 1H NMR spectroscopy, NICS values, ACID calculations, and ICSS plots.

Synthetic Anion Transporters as Endoplasmic Reticulum (ER) Stress Inducers.

Cl--ion transporters (2a-2h) were synthesized based on the binding motifs of prodigiosin. Transporter 2e clearly displays Cl--ion transportation activity across both model and live cell membranes. Furthermore, 2e can disrupt Ca2+ homeostasis and increase the intracellular concentration of Ca2+ in the DLD-1 cell. This disruption can lead to Caspase-dependent apoptosis supported by CHOP expression (a marker of ER stress) and the appearance of the cleaved forms of Caspase 3 and PARP.

Bond Rotation in an Aromatic Carbaporphyrin: Allyliporphyrin.

Allyliporphyrin is a carbaporphyrin that has replaced one pyrrole with an allyl group. Dynamic behavior (bond rotation) was observed by variable temperature 1 H NMR and 2D-NOESY NMR spectroscopy and theoretically examined by DFT calculations. These studies revealed that well-defined bond rotation was first observed in the limited space of the carbaporphyrin from 2 through cis-2 and the calculated rotational barrier was low enough, with the relative energy level of cis-2 only 0.65 kcal mol-1 higher than 2. The synthesized allyliporphyrin (2) is a strongly aromatic macrocycle as indicated by the chemical shifts of its inner NH and CH signals. However, its palladium complex displayed reduced aromaticity due to the tilted thiophene of Pd-2.

Synthesis of a Phlorin from a Meso-Fused Anthriporphyrin by a Diels-Alder Strategy.

An anthracene-containing meso-fused carbaporphyrin, which has extended π-conjugation pathways as compared to the corresponding naphthalene-containing carbaporphyrin, has been synthesized. The weak global aromaticity of the anthriporphyrin also allowed its use as the diene for a Diels-Alder reaction with dimethyl acetylenedicarboxylate (DMAD). The resulting phlorin contains an interesting bicyclic structure. Moreover, to the best of our knowledge, this phlorin is the first Diels-Alder adduct of a diene forming part of the global π-conjugation pathway of an aromatic porphyrinoid.

2-(Naphthalen-1-yl)thiophene as a New Motif for Porphyrinoids: Meso-Fused Carbaporphyrin.

The first synthesis of meso-fused carbaporphyrin via a premodification method was accomplished by substituting two pyrrole moieties and one meso-carbon with 2-(naphthalen-1-yl)thiophene. The obtained global π-conjugation pathway of the macrocycle noticeably disturbs the 10π local aromaticity of naphthalene, and its aromatic nature was supported by NMR spectroscopy together with nucleus-independent chemical shift, anisotropy of the induced current density, and harmonic oscillator stabilization energy calculations. In addition, the meso-fused carbaporphyrin also allowed the formation of a square planar Pd(II) complex.