Charge Transfer Modulated Self-Assembly in Poly(aryl ether) Dendron Derivatives with Improved Stability and Transport Characteristics.

Alteration of native gelation properties of anthracene and pyrene cored first generation poly(aryl ether) dendrons, G1-An and G1-Py, by introducing a common acceptor, 2,4,7-trinitro-9H-fluoren-9-one (TNF), results in forming charge transfer gels in long chain alcoholic solvents. This strategy leads to significant perturbation of optical and electronic properties within the gel matrix. Consequently, a noticeable increase of their electrical conductivities is observed, making these poly(aryl ether) dendron based gels potential candidates for organic electronics. While the dc-conductivity (σ) value for the native gel from G1-An is 2.8 × 10-4 S m-1, the value increased 3 times (σ = 8.7 × 10-4 S m-1) for its corresponding charge transfer gel. Further, the dc-conductivity for the native gel self-assembled from G1-Py dramatically enhanced by approximately an order of magnitude from 4.9 × 10-4 to 1.3 × 10-3 S m-1, under the influence of an acceptor. Apart from H-bonding and π···π interactions, charge transfer results in the formation of a robust 3D network of fibers, with improved aspect ratio, providing high thermo-mechanical stability to the gels compared to the native ones. The charge transfer gels self-assembled from G1-An/TNF (1:1) and G1-Py/TNF exhibit a 7.3- and 2.5-fold increase in their yield stress, respectively, compared to their native assemblies. A similar trend follows in the case of their thermal stabilities. This is attributed to the typical bilayer self-assembly of the former which is not present in the case of G1-Py/TNF charge transfer gel. Density functional calculations provide deeper insights accounting for the role of charge transfer interactions in the mode of self-assembly. The 1D potential energy surface for the G1-An/TNF dimer and G1-Py/TNF dimer is found to be 11.8 and 1.9 kcal mol-1 more stable than their corresponding native gel dimers, G1-An/G1-An and G1-Py/G1-Py, respectively.