Tuning the electronic nature of mono-bay alkynyl-phenyl-substituted perylene bisimides: synthesis, structure, and photophysical properties.

Perylene bisimide (PBI) derivatives with various alkynyl-phenyl substituents at a single bay position have been synthesised by Sonogashira coupling. NMR spectroscopic studies reveal the unsymmetric nature of the dyads. All of the dyads undergo two reversible reductions, which demonstrates their structural and electrochemical rigidity. The synthesised dyads show a remarkable redshift in their absorption maxima and sharp vibronic progression. Electron-rich substituents facilitate efficient charge transfer from the substituent HOMO to the electron-deficient PBI core. The most interesting spectral signatures were exhibited by a PBI with a strongly electron-donating ethynyl(dimethylaminophenyl) substituent. The steady-state features of this PBI showed a broad absorption that covered almost the whole visible region with no emission. A twisted intramolecular charge-transfer (TICT) process, related to the rotational motion of ethynyl(dimethylaminophenyl) PBI, was also demonstrated. Computational investigations shed light on the coplanarity of the various substituents with respect to the PBI core; the PBI core itself remains flat without any noticeable deformation even after mono-functionalisation. This illustrates that mono-functionalisation exerts meagre steric hindrance on the bay positions relative to disubstituted analogues. Despite several previous reports on the structural characterisation of 1,7-disubstituted PBI derivatives, we present the first structural characterisation of a mono-bay ethynyl-phenyl substituted PBI. The solid-state structure of the phenyl derivative has a flat PBI core without any noticeable steric constraints from the substituents, as predicted. In contrast, single-crystal X-ray analysis for the mono-bromo bay-substituted PBI shows that the bromine substituent is not in the plane of the PBI core.