Linker precursorsNDA via DBrNDA, DBrNDI and 2,6-dipyrrolo-NDI intermediates
Solventsconcentrated H2SO4; AcOH; pyrrolidine; anhydrous DMAc; CHCl3/MeOH chromatography solvent
Additivesdibromoisocyanuric acid; NH4OAc; 4-pyridinylboronic acid; Cu(OAc)2; Et3N; molecular sieves (4 A)
AtmosphereO2 purge 30 min and O2 environment for final Cu(II)-mediated coupling; earlier steps not specified
Temperature100 for DBrNDA; reflux for DBrNDI and dipyrrolo-NDI; 55 for final coupling
Time15; 3; 16; final 5 d total
Oxidant / reductantdibromoisocyanuric acid bromination reagent; Cu(OAc)2/O2-mediated coupling
Work-upDBrNDA filtered and washed with H2O/hot MeOH; DBrNDI filtered and washed with AcOH/diethyl ether; dipyrrolo-NDI washed with hexanes/MeOH; final product filtered, DMF-washed, hot CHCl3-extracted, and purified by SiO2 chromatography.
ActivationNot applicable for molecular ligand; isolated as navy-blue solid.
Scalability contextGram-scale intermediates; final BPDPNDI 0.72 g, yield ≈ 40%.
Show 10 structured reagent records
| Role | Reagent | Amount / concentration | Source |
|---|
| Linker | NDA | 2.68 g, 10 mmol | S1-S2 · II. Synthesis of and Characterization of BPDPNDI Pillar · Scheme S1 |
| Oxidant | dibromoisocyanuric acid | 11.48 g, 20 mmol | S1-S2 · II. Synthesis of and Characterization of BPDPNDI Pillar · Scheme S1 |
| Acid | concentrated H2SO4 | 10 mL + 10 mL · concentrated | S1-S2 · II. Synthesis of and Characterization of BPDPNDI Pillar · Scheme S1 |
| Additive | NH4OAc | 15.5 g, 188 mmol | S1-S2 · II. Synthesis of and Characterization of BPDPNDI Pillar · Scheme S1 |
| Solvent | AcOH | 40 mL | S1-S2 · II. Synthesis of and Characterization of BPDPNDI Pillar · Scheme S1 |
| Additive | pyrrolidine | 20 mL | S1-S2 · II. Synthesis of and Characterization of BPDPNDI Pillar · Scheme S1 |
| Linker | 4-pyridinylboronic acid | 3.96 g, 32.3 mmol plus 1.98 g, 16.2 mmol | S1-S2 · II. Synthesis of and Characterization of BPDPNDI Pillar · Scheme S1 |
| Oxidant | Cu(OAc)2 | 5.83 g, 32.3 mmol plus 2.92 g, 16.2 mmol | S1-S2 · II. Synthesis of and Characterization of BPDPNDI Pillar · Scheme S1 |
| Base | Et3N | 4.5 mL, 32.3 mmol plus 2.3 mL, 16.2 mmol | S1-S2 · II. Synthesis of and Characterization of BPDPNDI Pillar · Scheme S1 |
| Solvent | anhydrous DMAc | 100 mL plus 25 mL | S1-S2 · II. Synthesis of and Characterization of BPDPNDI Pillar · Scheme S1 |