Photoinduced tuning of (anti)aromaticity and associated molecular properties is currently in the focus of attention for both tailoring photochemical reactivity and designing new materials. Here, we report on the synthesis and spectroscopic characterization of diarylethene-based molecular switches embedded in a biphenylene structure composed of rings with different levels of local (anti)aromaticity. We show that it is possible to modulate and control the (anti)aromatic character of each ring through reversible photoswitching of the aryl units of the system between open and closed forms. Remarkably, it is shown that the irreversible formation of an annulated bis(dihydro-thiopyran) side-product that hampers the photoswitching can be efficiently suppressed when the aryl core formed by thienyl groups in one switch is replaced by thiazolyl groups in another.

The synthesis and properties of a series of unsymmetrical thienopentalenes are explored, including both monoareno and diareno derivatives. For the synthesis of monoareno pentalenes, a carbopalladation cascade reaction between alkynes and gem-dibromoolefins was applied. Diareno pentalene derivatives were accessed via gold-catalyzed cyclization of diynes. Thiophene was fused to pentalene in two different geometries via its 2,3 and 3,4 bonds. 2,3-Fusion resulted in increased antiaromaticity of the pentalene unit compared to the 3,4-fusion both in the monoareno and diareno framework. Monothienopentalenes that contained the destabilizing 2,3-fusion could not be isolated. For diareno derivatives, the aromatic character of the different aryl groups fused to the pentalene was not independent. Destabilizing fusion on one side resulted in alleviated aromaticity on the other side and vice versa. The synthesized molecules were characterized experimentally by 1H NMR and UV–vis spectroscopies, cyclic voltammetry, and X-ray crystallography, and their aromatic character was assessed using magnetic (NICS and ACID) and electronic indices (MCI and FLU).