4 iodobenzoic acid

Reagent
grade carbazole, p-bromonitrobenzene, copper iodide,
1,10-phenantroline, potassium
carbonate, hydrazine monohydrate, pyridine, acetic anhydride, cesium
carbonate, palladium on charcoal, tetrabutyl ammonium hexafluorophosphate
(TBAPF₆), FeCl₃, 4-iodoaniline, 4-iodobenzoic
acid, Cu₂O, and 1,4,5,8-naphthalenetetracarboxylic dianhydride
were purchased from Sigma-Aldrich and were used as-received. Reagent
grade 1,2-cyclohexane anhydride and 1,2,4,5-cyclohexane dianhyride
were purchased from TCI Co., Ltd. and used as-received. Amino-phenyl
carbazole (APC) was stored as its HCl salt (Supporting Information, SI), and liberated before
use. Compound D1 is the precursor to the APC·HCl salt. Compound D2 was synthesized through
esterification of p-iodobenzoic acid followed by
cuprous oxide mediated carbazole coupling (SI). Details of the synthesis and characterization of APCCDI and APCNDI are provided as SI (Figures S1–S18).
UV/vis
absorption spectroscopy, electrochemistry, in situ UV/vis absorption,
and resonance Raman spectroelectrochemical experiments were conducted
in spectroscopic (UVASOL) grade dichloromethane (Merck).

Sodium tetrachloropalladate(II) (Na₂PdCl₄, 99.995%), gold(III) chloride hydrate (HAuCl₄, ≥49% Au basis), sodium hydroxide (NaOH, ≥98%), sodium borohydride (NaBH₄, ≥99%) cetyltrimethylammonium bromide (CTAB, ≥99%), ascorbic acid (≥99.0%), 1-hydroxybenzotriazole hydrate (HOBt, 99%), N,N’-diisopropylcarbodiimide (DIC, 99%), acetic anhydride (Ac₂O, 99.5%), ethanol (≥99.5%), methanol (MeOH, ≥99.5%), 1-octanol (≥99%), dichloromethane (CH₂Cl₂, ≥99.9%), ethyl acetate (EtOAc, 99.8%), tetrahydrofuran (THF, ≥99.9%), ethylene glycol (EG, ≥99%), N,N-dmethylformamide (DMF, ≥99%), pyridine (≥99.9%), iodobenzene (98%), 4-iodotoluene (≥99%); 4-iodobenzoic acid (98%), biphenyl-4-carboxamide (96%), phenylboronic acid (PhB(OH)₂, >98%), deuterated chloroform (CDCl₃, 99.8%), deuterated dimethyl sulfoxide (DMSO-d6, 99.9%), trifluoroacetic acid (TFA, ≥99.0%), potassium carbonate (K₂CO₃, ≥99.0%) and magnesium sulfate (MgSO₄, ≥99.5%) were all purchased from Sigma-Aldrich, and used as received without further purification except THF which was distilled to remove tutylated hydroxytoluene (BHT). NovaSyn TGR resin (0.25 mmol/g loading) was purchased from EMD Millipore. Sartorius ultrapure water (18.2 MΩ•cm) was used in all preparations.