We have investigated the ultrafast dynamics of o-, m- and p-bisazobenzenes, which represent elementary building blocks for photoswitchable multiazobenzene nanostructures. The connectivity pattern within bisazobenzenes and the ensuing complex interactions between the individual azobenzene units determines the ultrafast dynamics of these compounds and their photochemical properties. While retaining a relatively high E → Z isomerization quantum yield, o-bisazobenzene exhibits a very high thermal relaxation rate (half-life of 1.6 ms). Our theoretical calculations reveal that the geometry allows intramolecular excitonic interaction between the azobenzene units, which is reflected in the femtosecond transient absorption data via the simultaneous bleaching of the two excitonic bands. In contrast, the properties of m-bisazobenzene are very similar to the monomeric azobenzene, with the two units acting nearly independently from each other. The highest degree of π conjugation extending over the two azobenzene units was observed for p-bisazobenzene, which results in strong planarity of the molecule, reduced excited state lifetime and relatively low isomerization quantum yield. Multiphotochromic systems bridge the gap between molecular photoswitches and macroscopic function and thus, understanding the properties of bisazobenzenes opens the way to the design and development of new structures with extensive and versatile applications.

Azoheteroarene photoswitches have attracted attention due to their unique properties. We present the stationary photochromism and ultrafast photoisomerization mechanism of thiophenylazobenzene (TphAB). It demonstrates impressive fatigue resistance and photoisomerization efficiency, and shows favorably separated (E)‐ and (Z)‐isomer absorption bands, allowing for highly selective photoconversion. The (Z)‐isomer of TphAB adopts an unusual orthogonal geometry where the thiophenyl group is perfectly perpendicular to the phenyl group. This geometry is stabilized by a rare lone‐pair⋅⋅⋅π interaction between the S atom and the phenyl group. The photoisomerization of TphAB occurs on the sub‐ps to ps timescale and is governed by this interaction. Therefore, the adoption and disruption of the orthogonal geometry requires significant movement along the inversion reaction coordinates (CNN and NNC angles). Our results establish TphAB as an excellent photoswitch with versatile properties that expand the application possibilities of AB derivatives.

meta-Trisazobenzenes allow for wavelength-selective photo-switching of the individual azobenzene branches.

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Continuous irradiation of the thermodynamically stable ( Z, Z)-cyclobisazobenzene does not lead to accumulation of a ( Z, E) or ( E, E) isomer as one might expect. Our combined experimental and computational investigation reveals that Z → E photoisomerization still takes place on an ultrafast time scale but induces large ring strain in the macrocycle, which leads to a very fast thermal back-isomerization, preventing photostationary accumulation of ( E)-isomers.

Azobenzenes are widely utilized as molecular photoswitches for control of nanoscale processes. Their photoisomerization reaction is highly robust and is retained even in extremely rigid systems. Currently, it is not clear what geometric restrictions are required to block this isomerization successfully. We present here a combined experimental and theoretical study on the ultrafast dynamics of cyclotrisazobenzene (CTA) and demonstrate that the structural constraints in CTA prevent isomerization of the photoswitch units. In the developed molecular picture, the N=N bonds respond elastically to the motion along the isomerization coordinates, which leads to ultrafast and complete dissipation of the UV excitation as heat. Based on this property, CTA and possibly other similarly designed molecules can be utilized as UV absorbers, for example in sunscreens; other potential applications are also envisioned.