An ambient stable core-substituted perylene bisimide dianion: isolation and single crystal structure analysis

Abstract

The reduction of a highly electron deficient PBI afforded the corresponding dianion disodium salt that was characterized by single crystal structure analysis.

Twisted Perylene Diimides with Tunable Redox Properties for Organic Sodium‐Ion Batteries

“…δP decreases from 524 mV in 1 to 302 mV in 2 and 242 mV in 3 beyond which the peaks merge and appear as a broad peak in 4 and as a single sharp peak in 5 (Table ). These findings are in excellent agreement with the trend observed in solvent dependent cyclic voltammograms studied in the earlier report . 4 and 5 , as observed in the ΔG values, show a better reduction potential than 1–3, which is attributed to the proportional increase in the cell potential with the change in free energy.…”

“…The practical capacities corresponding to almost two sodium ion insertion along with the single redox pair obtained from discharge capacity plots led us to predict a single step redox mechanism for 5 as shown in Figure d. The proposed mechanism corroborates with the theoretical calculations and the report in literature on solvent dependent cyclic voltammetry for perylene diimides …”

Twisted Perylene Diimides with Tunable Redox Properties for Organic Sodium‐Ion Batteries

“…δP decreases from 524 mV in 1 to 302 mV in 2 and 242 mV in 3 beyond which the peaks merge and appear as a broad peak in 4 and as a single sharp peak in 5 (Table ). These findings are in excellent agreement with the trend observed in solvent dependent cyclic voltammograms studied in the earlier report . 4 and 5 , as observed in the ΔG values, show a better reduction potential than 1–3, which is attributed to the proportional increase in the cell potential with the change in free energy.…”

“…The practical capacities corresponding to almost two sodium ion insertion along with the single redox pair obtained from discharge capacity plots led us to predict a single step redox mechanism for 5 as shown in Figure d. The proposed mechanism corroborates with the theoretical calculations and the report in literature on solvent dependent cyclic voltammetry for perylene diimides …”

Substituent-dependent absorption and fluorescence properties of perylene bisimide radical anions and dianions

“…At least two reversible reduction waves are observed for all five derivatives. Values range from À0.14 V for the first reduction and À0.48 V for the second reduction of the strongest electron acceptor PBI-ClCN, which are in line with the reported values for a derivative thereof, 29 to À1.10 V and À1.29 V for the first and second reduction waves, respectively, for the weakest electron acceptor PBI-OPh. 45 The other derivatives follow the expected sequence by exhibiting their first reduction wave at À0.77 V for PBI-Cl, À1.00 V for PBI-H and À1.02 V for PBI-Ph, respectively.…”

Lowering Electrocatalytic CO 2 Reduction Overpotential Using N-Annulated Perylene Diimide Rhenium Bipyridine Dyads with Variable Tether Length

“…At the same time, two strong absorption bands appeared at 617 and 652 nm. The observed orange to green to blue color change was consistent for bpy-C2-NPDI , Re­(bpy-C4-NPDI) , and Re­(bpy-C6-NPDI) (Figures S92–S95), further confirming the assignment of the PDI 0/•– and PDI •–/2– reductions. , Moreover, application of potentials of −0.9 V (R1) and −1.2 V (R2) led to similar UV–vis-nIR SEC responses for Re­(py-C0-NPDI) (Figure S96). However, differences in the absorption profiles of Re­(py-C0-NPDI) vs Re­(bpy-C2/4/6-NPDI) meant each transition was broadened and found to occur at a slightly blue-shifted λ max .…”

Twisted Perylene Diimides with Tunable Redox Properties for Organic Sodium‐Ion Batteries

“…δP decreases from 524 mV in 1 to 302 mV in 2 and 242 mV in 3 beyond which the peaks merge and appear as a broad peak in 4 and as a single sharp peak in 5 (Table ). These findings are in excellent agreement with the trend observed in solvent dependent cyclic voltammograms studied in the earlier report . 4 and 5 , as observed in the ΔG values, show a better reduction potential than 1–3, which is attributed to the proportional increase in the cell potential with the change in free energy.…”

“…The practical capacities corresponding to almost two sodium ion insertion along with the single redox pair obtained from discharge capacity plots led us to predict a single step redox mechanism for 5 as shown in Figure d. The proposed mechanism corroborates with the theoretical calculations and the report in literature on solvent dependent cyclic voltammetry for perylene diimides …”

Substituent-dependent absorption and fluorescence properties of perylene bisimide radical anions and dianions

“…At least two reversible reduction waves are observed for all five derivatives. Values range from À0.14 V for the first reduction and À0.48 V for the second reduction of the strongest electron acceptor PBI-ClCN, which are in line with the reported values for a derivative thereof, 29 to À1.10 V and À1.29 V for the first and second reduction waves, respectively, for the weakest electron acceptor PBI-OPh. 45 The other derivatives follow the expected sequence by exhibiting their first reduction wave at À0.77 V for PBI-Cl, À1.00 V for PBI-H and À1.02 V for PBI-Ph, respectively.…”

Lowering Electrocatalytic CO 2 Reduction Overpotential Using N-Annulated Perylene Diimide Rhenium Bipyridine Dyads with Variable Tether Length

“…At the same time, two strong absorption bands appeared at 617 and 652 nm. The observed orange to green to blue color change was consistent for bpy-C2-NPDI , Re­(bpy-C4-NPDI) , and Re­(bpy-C6-NPDI) (Figures S92–S95), further confirming the assignment of the PDI 0/•– and PDI •–/2– reductions. , Moreover, application of potentials of −0.9 V (R1) and −1.2 V (R2) led to similar UV–vis-nIR SEC responses for Re­(py-C0-NPDI) (Figure S96). However, differences in the absorption profiles of Re­(py-C0-NPDI) vs Re­(bpy-C2/4/6-NPDI) meant each transition was broadened and found to occur at a slightly blue-shifted λ max .…”

Twisted Perylene Diimides with Tunable Redox Properties for Organic Sodium‐Ion Batteries

“…δP decreases from 524 mV in 1 to 302 mV in 2 and 242 mV in 3 beyond which the peaks merge and appear as a broad peak in 4 and as a single sharp peak in 5 (Table ). These findings are in excellent agreement with the trend observed in solvent dependent cyclic voltammograms studied in the earlier report . 4 and 5 , as observed in the ΔG values, show a better reduction potential than 1–3, which is attributed to the proportional increase in the cell potential with the change in free energy.…”

“…The practical capacities corresponding to almost two sodium ion insertion along with the single redox pair obtained from discharge capacity plots led us to predict a single step redox mechanism for 5 as shown in Figure d. The proposed mechanism corroborates with the theoretical calculations and the report in literature on solvent dependent cyclic voltammetry for perylene diimides …”

Substituent-dependent absorption and fluorescence properties of perylene bisimide radical anions and dianions

“…At least two reversible reduction waves are observed for all five derivatives. Values range from À0.14 V for the first reduction and À0.48 V for the second reduction of the strongest electron acceptor PBI-ClCN, which are in line with the reported values for a derivative thereof, 29 to À1.10 V and À1.29 V for the first and second reduction waves, respectively, for the weakest electron acceptor PBI-OPh. 45 The other derivatives follow the expected sequence by exhibiting their first reduction wave at À0.77 V for PBI-Cl, À1.00 V for PBI-H and À1.02 V for PBI-Ph, respectively.…”

Lowering Electrocatalytic CO 2 Reduction Overpotential Using N-Annulated Perylene Diimide Rhenium Bipyridine Dyads with Variable Tether Length

“…At the same time, two strong absorption bands appeared at 617 and 652 nm. The observed orange to green to blue color change was consistent for bpy-C2-NPDI , Re­(bpy-C4-NPDI) , and Re­(bpy-C6-NPDI) (Figures S92–S95), further confirming the assignment of the PDI 0/•– and PDI •–/2– reductions. , Moreover, application of potentials of −0.9 V (R1) and −1.2 V (R2) led to similar UV–vis-nIR SEC responses for Re­(py-C0-NPDI) (Figure S96). However, differences in the absorption profiles of Re­(py-C0-NPDI) vs Re­(bpy-C2/4/6-NPDI) meant each transition was broadened and found to occur at a slightly blue-shifted λ max .…”