Co-reporter:Denan Wang, Marat R. TalipovMaxim V. Ivanov, Rajendra Rathore
Journal of the American Chemical Society 2016 Volume 138(Issue 50) pp:16337-16344
Publication Date(Web):November 23, 2016
DOI:10.1021/jacs.6b09209
Poly-p-phenylene wires are critically important as charge-transfer materials in photovoltaics. A comparative analysis of a series of poly-p-phenylene (RPPn) wires, capped with isoalkyl (iAPPn), alkoxy (ROPPn), and dialkylamino (R2NPPn) groups, shows unexpected evolution of oxidation potentials, i.e., decrease (−260 mV) for iAPPn, while increase for ROPPn (+100 mV) and R2NPPn (+350 mV) with increasing number of p-phenylenes. Moreover, redox/optical properties and DFT calculations of R2NPPn/R2NPPn+• further show that the symmetric bell-shaped hole distribution distorts and shifts toward one end of the molecule with only 4 p-phenylenes in R2NPPn+•, while shifting of the hole occurs with 6 and 8 p-phenylenes in ROPPn+• and iAPPn+•, respectively. Availability of accurate experimental data on highly electron-rich dialkylamino-capped R2NPPn together with ROPPn and iAPPn allowed us to demonstrate, using our recently developed Marcus-based multistate model (MSM), that an increase of oxidation potentials in R2NPPn arises due to an interplay between the electronic coupling (Hab) and energy difference between the end-capped groups and bridging phenylenes (Δε). A comparison of the three series of RPPn with varied Δε further demonstrates that decrease/increase/no change in oxidation energies of RPPn can be predicted based on the energy gap Δε and coupling Hab, i.e., decrease if Δε < Hab (i.e., iAPPn), increase if Δε > Hab (i.e., R2NPPn), and minimal change if Δε ≈ Hab (i.e., ROPPn). MSM also reproduces the switching of the nature of electronic transition in higher homologues of R2NPPn+• (n ≥ 4). These findings will aid in the development of improved models for charge-transfer dynamics in donor–bridge–acceptor systems.
Co-reporter:Vijay S. Vyas and Rajendra Rathore
Chemical Communications 2010 vol. 46(Issue 7) pp:1065-1067
Publication Date(Web):12 Jan 2010
DOI:10.1039/B923915D
Soluble tetrakis(pentaphenylphenyl)ethylene (1), prepared in three steps, allows non-emissive tetraphenylethylene (TPE) to turn into an emitter (ΦF = 0.13) owing to the steric bulk of the four large hexaphenylbenzene propellers which hamper C–Ph and CC bond rotations in the TPE core.
Co-reporter:Vijay S. Vyas and Rajendra Rathore
Chemical Communications 2010 - vol. 46(Issue 7) pp:NaN1067-1067
Publication Date(Web):2010/01/12
DOI:10.1039/B923915D
Soluble tetrakis(pentaphenylphenyl)ethylene (1), prepared in three steps, allows non-emissive tetraphenylethylene (TPE) to turn into an emitter (ΦF = 0.13) owing to the steric bulk of the four large hexaphenylbenzene propellers which hamper C–Ph and CC bond rotations in the TPE core.