Diazocines, bridged azobenzenes, exhibit superior photophysical properties compared to parent azobenzenes such as high switching efficiencies, quantum yields, and particularly switching wavelengths in the visible range. Synthesis, however, proceeds with low yields, and derivatives are difficult to prepare. We now present two heterodiazocines which are easier to synthesize, and the general procedures should also provide facile access to derivatives. Moreover, both compounds can be switched with light in the far-red (650 nm). Accessibility and photophysical properties make them ideal candidates for applications such as photoswitchable drugs and functional materials.

The reactivity of the renewable amide 3-acetamido-5-acetylfuran (3A5AF) was explored. Hydrolysis of the amido group to yield the amino-substituted furan, 2-acetyl-4-aminofuran (1), was achieved via NaOH catalysis. Reduction of the acetyl group could be achieved stoichiometrically using NaBH4 or catalytically via transfer hydrogenation using an Ir catalyst. The product alcohol, 3-acetamido-5-(1-hydroxylethyl)­furan (2), underwent dehydration during analysis via GC-MS to yield an alkene (3). The potential reactivity of 3A5AF and 1 toward carbon dioxide was studied, but no reaction was observed due to the inherent acidity of 3A5AF and 1 despite the latter being an amine. The computationally determined pK a values for 3A5AF and 1 are reported. Interestingly, in this work, tautomerism of 3A5AF was observed in CD3OD as evidenced by H–D exchange within the acetyl group.

The incorporation of molecular machines into the backbone of porous framework structures will facilitate nano actuation, enhanced molecular transport, and other out-of-equilibrium host-guest phenomena in well-defined 3D solid materials. In...

Overcrowded alkene based molecular motors and switches constitute a unique class of photo-responsive systems due to their intrinsic chirality next to the core C=C bond, making them highly suitable candidates...

10,15,20-Tris(pentafluorophenyl)-substituted Ni -porphyrin meso-oxy radical bearing two coordinating pyridines was synthesized as a stable radical with a quartet ground state (S=3/2). X-ray structural analysis revealed that the Ni porphyrin moiety is fairly planar and the Ni-N bond lengths are considerably longer, indicating the high-spin state of the Ni center. The radical exhibited a quartet ground state, indicating the ferromagnetic interaction between the high-spin Ni center (S=1) and the porphyrin meso-oxy radical (S=1/2).