Deciphering Internal and External π-Conjugation in C3 -Symmetric Multiple Azobenzene Connected Systems in Self-Assembly.

Two tripodal C3 -symmetric photoswitchable molecular systems T1 and T2 are reported that have extended conjugation at external and internal positions using an acryl group. The influence of the extended π-bonds in their absorption properties, thermal relaxation of the photoisomers and their propensities in forming supramolecular self-assemblies have been explored through spectroscopy, and microscopic studies. In particular, the investigations on the self-assembly have been carried out using scanning electron microscopy (SEM), transmission electron microscopy (TEM), polarized optical microscopy (POM), X-ray diffraction studies (XRD) and atomic force microscopy (AFM). Remarkably, the position of the acryl group influences the behaviour of the two target molecules in supramolecular assembly, and also in the formation of photoresponsive organic hydrogels or microcrystals.

The curious case of the photochemistry of 2-hydroxyphenylazo-3,5-dimethylisoxazole: unravelling the process among tautomerization, photoisomerization, and conformational changes.

Considering the growing interest in azoheteroarene photoswitches, the molecular level process underlying photochemistry is intriguing. In our earlier investigation on phenylazo-3,5-dimethylisoxazole, besides E-Z photoisomerization, we also observed light-induced phase transition that supports the possible conformational changes under neat conditions. Furthermore, hydrogen bond-forming groups such as -OH, at the ortho position to the azo chromophore, can potentially hamper the isomerization through tautomerism. All of them develop a curiosity in the photochemical outcome of 2-hydroxyphenylazo-3,5-dimethylisoxazole (HPAI, 1). Herein, we report the photochemistry of HPAI in an argon matrix at 4 K, followed by infrared spectroscopy. Through experiments and computations, we identified the E-Z photoisomerization in HPAI as the only observed channel among the above-mentioned possibilities.

Bu4NI-Catalyzed, Radical-Induced Regioselective N-Alkylations and Arylations of Tetrazoles Using Organic Peroxides/Peresters.

Bu4NI-catalyzed regioselective N2-methylation, N2-alkylation, and N2-arylation of tetrazoles have been achieved using tert-butyl hydroperoxide (TBHP) as the methyl source, alkyl diacyl peroxides as the primary alkyl source, alkyl peresters as the secondary and tertiary alkyl sources, and aryl diacyl peroxides as the arylating source. These reactions proceed without pre-functionalization of tetrazole and in the absence of any metal catalysts. Here, peroxides serve the dual role of oxidants as well as alkylating or arylating agents. Based on DFT calculations, it was found that spin density, transition-state barriers (kinetic control), and thermodynamic stability of the products (thermodynamic control) play essential roles in the observed regioselectivity during N-alkylation. This radical-mediated process is amenable to a broad range of substrates and provides products in moderate to good yields.

Arylazo-3,5-dimethylisoxazoles: Azoheteroarene Photoswitches Exhibiting High Z-Isomer Stability, Solid-State Photochromism, and Reversible Light-Induced Phase Transition.

Reversibly photoswitchable phenylazo-3,5-dimethylisoxazole and 37 aryl-substituted derivatives were synthesized. Excellent photoswitching ability of these compounds in solution and the solid state was demonstrated. Through kinetics studies by means of NMR spectroscopy, high Z-isomer stability was demonstrated. Interestingly, the majority of the derivatives showed light-induced contrasting color changes in solution and the solid state. Besides, many of the derivatives exhibit partial phase transition upon UV irradiation. The highlight of this class of photoswitches is the reversible light-induced phase transition between solid and liquid phases in the parent compound, which can be used in patterned crystallization. These results show that this new class of azoheteroarene based photoswitches has opportunities to be useful in various domains.

Deciphering Stability of Five-Membered Heterocyclic Radicals: Balancing Act Between Delocalization and Ring Strain.

Computational studies on five-membered heterocycles with single heteroatom and their isomeric dehydro-borole 1a-1c, cyclopentadiene 2a-2c, pyrrole 3a-3c, furan 4b-4c, phosphole 5a-5c, and thiophene 6b-6c radicals have been carried out. Geometrical aspects through ground state electronic structures and stability aspects using bond dissociation energies (BDE) and radical stabilization energies (RSE) have been envisaged in this regard. Spin densities, electrostatic potentials (ESP), and natural bond orbital (NBO) analysis unveiled the extent of spin delocalization. The estimated nucleus-independent chemical shifts (NICS) values revealed the difference in aromaticity characteristics of radicals. Particularly the heteroatom centered radicals exhibit odd electron π-delocalized systems with a quasi-antiaromatic character. Various factors such as, the relative position of the radical center with respect to heteroatoms, resonance, ring strain and orbital interactions influence the stability that follows the order: heteroatom centered > ß-centered > α-centered radicals. Among the influences of various factors, we confirmed the existence of a competition between delocalization and the ring strain, and the interplay of both decides the overall stability order.

Does a Nitrogen Lone Pair Lead to Two Centered-Three Electron (2c-3e) Interactions in Pyridyl Radical Isomers?

Each of the three isomeric pyridyl radicals (2-, 3-, and 4-dehydropyridines) contains a lone pair and an unpaired electron. As a result, a potential two centered-three electron interaction between the radical electron and the lone pair through-space (TS) and/or through-bond (TB) can exist that may influence the stability of the radicals. Due to the change in geometrical positions relative to each other, the strength of interaction can be varied. In this study, we investigated the structural and stability aspects of pyridyl radical isomers with a major emphasis on the interaction of a nitrogen lone pair with the radical center. In order to obtain evidence for such interactions, protonated and N-oxide analogues of the corresponding isomeric pyridyl radicals have been considered in such a way to understand the consequences due to unavailability of the lone pair. Similarly, electron attachment and detachment energies at the radical center (vertical detachment energy, VDE, of corresponding anions and vertical ionization energy, VIE, of radical isomers) have been calculated to find out the interaction trend upon modification at the radical center. Different levels of theory including (U)B3LYP/cc-pVTZ, (U)M06/cc-pVTZ, CBS-QB3, single-point energy calculations at (U)CCSD(T)/cc-pVTZ, and multireference CASSCF/cc-pVTZ methods have been employed in this regard. A closer inspection of geometries, relative stability order, spin density, electrostatic potential, molecular orbitals, NBO analysis, and vibrational analysis have showed a strong and stabilizing TS interaction between the radical center and the lone pair in the case of the 2-pyridyl radical. On the other hand, the 4-pyridyl radical showed stabilizing interactions only via TB coupling, whereas the TS interaction is nonexistent. Despite the presence of both interactions in the case of the 3-pyridyl radical, their overall influence is less effective toward stability.