Synthesis and Photophysical Properties of Novel Meta-Conjugated Organic Molecules with 1,3,5-Benzene Branching Units

Abstract

The synthesis and photophysical investigation of three novel meta-conjugated molecules based on 3,1,2-benzothiadiazole and thiophene-2,5-diyl derivatives linked through 1,3,5-benzene branching units are described. Each of them is a symmetrical molecule with two branching units, four identical lateral thiophene-containing fragments, and one central benzothiadiazole-containing fragment. To study the effect of the chemical structure on their photophysical properties, the molecules with different linearly conjugated lateral and central fragments due to incorporation of additional thiophene rings were synthesized and compared. It was shown that absorption spectra of the meta-conjugated molecules can be represented as a sum of absorption bands of model compounds for their peripheral and central fragments containing a common benzene ring being branched at the 1,3,5-benzene unit in the meta-conjugated molecules. Therefore, they cannot be considered simply as isolated π-conjugated systems of their peripheral and central fragments. Instead, DFT calculations showed that several transitions between the orbitals located in different regions of the meta-conjugated molecule are responsible for the formation of their absorption spectra, and they strongly depend on the degree of their overlapping. Theoretical absorption spectra reconstructed from the DFT data demonstrated a good agreement with the experimental results: the transitions with larger oscillator strength correspond to the bands with higher molar extinction coefficients and vice versa. It was shown that luminescence spectral maxima of the meta-conjugated molecules monotonically shift to the lower energy from 489 to 540 and 613 nm with increasing the number of thiophene rings in the peripheral and central fragments, respectively. However, luminescence quantum yield of the meta-conjugated molecules critically depends on the length of linearly conjugated fragments in its structure decreasing from 24% to 1.3% with increasing the number of thiophene rings in the lateral fragments but increasing to 90% in the molecule with more thiophene rings in both types of the fragments. The results obtained are well correlated to the ratio of radiative and nonradiative deactivation rate constants of the meta-conjugated molecules that indicates a high rate of internal conversion between the excited states corresponding to different fragments of the molecule. The CV measurements allowed estimating the HOMO, LUMO, and bandgap values of the target and model compounds, which confirm the presence of meta-conjugation within the molecules investigated. Thus, connection of linearly conjugated fragments through meta-positions (meta-conjugation) of a benzene ring leads to an intermediate option between fully conjugated and nonconjugated molecules due to partial delocalization of electron density through the 1,3,5-substituted benzene branching center.