1 H-NMR (500 MHz, DMSO-d6): δ 10.55 (s, 4H), 9.04 (s, 2H), 8.49 (s, 4H), 8.54 (s, 4H), 7.99 (dd, J = 6.2, 3.3 Hz, 4H), 7.57 (dd, J = 6.2, 3.2 Hz, 4H). 13 C{ 1 H}-NMR (201 MHz, DMSO-d6): δ 163.9, 135.6, 130.8, 130.6, 130.0, 129.9 (q, 2 JCF = 33 Hz), 129.3, 127.8, 127.4, 126.2, 123.7, 123.6 (q, 1 JCF = 272 Hz). The reaction flask containing the 5-(trifluoromethyl)isophthaloyl dichloride (0.20250 g) was evacuated and charged with dry N2(g). The pre-dried TBACl (1.08590 g, 5 equivs.) was pre-dissolved in CH2Cl2 (20 mL). The CH2Cl2:TBACl solution (10 mL) was added directly to the reaction flask and allowed to stir for 10 min. The 1,2-diamino-4,5-difluorobenzene (0.12388 g, 1.1 equivs.) was also pre-dissolved in the CH2Cl2:TBACl solution (10 mL) and then added to the reaction mixture over 2 min. After a total of 10 min, the reaction was stopped, and the volatiles evaporated under reduced pressure. The crude material was then triturated in hot acetone (55 °C, 328.15 K). The mixture was allowed to cool to r.t. before being placed in the freezer at -20 °C (253.15 K), where a white precipitate of the Cl -complex formed over 48 h. The precipitate was separated and washed with H2O (excess) and n-hexane (4×10 mL) to remove residual diamine and excess TBACl. The filtrate was also collected, and the trituration process was repeated until no more solid precipitated from the solution. The collected solids were consolidated, and anion exchange was then performed by suspending the solid in CH3CN (25 mL), KPF6 (10 equivs.) was added, and the mixture was stirred for 12 h. The fine purple solid was filtered and washed with H2O (excess) before being dried in vacuo, with a final yield of 0.04066 g (8%). 4 5 ,10 5 -Di-tert-butyl-2,6,8,12-tetraaza-1,7(1,2),4,10(1,3)-tetrabenzenacyclododecaphane-3,5,9,11-tetraone (Tetralactam 4a) Tetralactam 4a was synthesised according to an adapted previously reported method. The TBACl (1.8890 g, 5 equivs.) was dried in vacuo for 1 h and dissolved in CH2Cl2 (30 mL, dry, degassed). First, the ortho-phenylenediamine (92.5 mg, 1.1 equivs.) was dissolved in CH2Cl2 (15 mL). The CH2Cl2:TBACl solution was added dropwise to the 5-tert-butylisophthaloyl dichloride (0.2017 g) under N2(g), and more CH2Cl2 (30 mL, dry, degassed) was added and allowed to stir for 0.5 h to ensure homogeneity. The reaction flask was re-evacuated with N2(g) before the diamine solution was added via syringe over 2 min. The reaction was allowed to stir for an extra 8 min before the reaction stopped, and the volatiles were removed under reduced pressure. The solid was then suspended in H2O (50 mL) and sonicated before a system of CH3CN:H2O (3:7, v/v) was added to the agitated mixture and cooled to 4 °C (277.15 K), produced to precipitate the crude product. The precipitate was then triturated in CHCl3 (100 mL, 60 °C), and the mixture was cooled to produce the chloride complex. The floating solid was collected, and anion exchange was then performed by resuspending the solid in H2O (150 mL) with KPF6 (10 equivs.) and stirred for 12 h. The solid was then filtered and washed with H2O (excess). The solid was dried in vacuo, resulting in a final yield of the white solid was 0.08155 g (18%). The reaction flask containing the 5-tert-butylisophthaloyl dichloride (0.06949 g) was evacuated and charged with dry N2(g). The pre-dried TBACl (0.35635 g, 5 equivs.) was pre-dissolved in CH2Cl2 (20 mL). The CH2Cl2:TBACl solution (10 mL) was added directly to the reaction flask and allowed to stir for 10 min. The 2,3-diaminonapthalene (0.04459 g, 1.1 equivs.) was predissolved in the CH2Cl2:TBACl solution (10 mL) and then added to the reaction mixture over 2 min. After a total of 10 min, the reaction was stopped, and the volatiles evaporated under reduced pressure. A system of n-hexane:CH3OH (8:2, v/v) was added to the crude solid, producing a brown precipitate formed at the interface between the solvents. This process was repeated until precipitation stopped. The collected solids were then dissolved in a mixture of CH2Cl2:CH3OH (2:1, v/v, 20 mL) and cooled to -20 °C for 24 h. The Cl -complex of the desired product was separated and resuspended in CH3OH (-20 °C, 10 mL) for 12 h before the solid was collected and dried. Anion exchange was then performed by suspending the solid in CH3CN (25 mL), KPF6 (10 equivs.) was added, and the mixture was stirred for 12 h. The fine purple solid was filtered and washed with H2O (excess) before being dried in vacuo, with a final yield of 0.02633 g (15%). The reaction flask containing the 5-tert-butylisophthaloyl dichloride (0.62662 g) was evacuated and charged with dry N2(g). The pre-dried TBACl (3.21289 g, 5 equivs.) was pre-dissolved in CH2Cl2 (20 mL). The CH2Cl2:TBACl solution (10 mL) was added directly to the reaction flask and allowed to stir for 10 min. The 1,2-diamino-4,5-difluorobenzene (0.36654 g, 1.1 equivs.) was also pre-dissolved in the CH2Cl2:TBACl solution (10 mL) and then added to the reaction mixture over 2 min. After a total of 10 min, the reaction was stopped, and the volatiles evaporated under reduced pressure H2O (15 mL) was added to the viscous oil-like crude material, and then a mixture of CH3CN:H2O (3:7, v/v, 35 mL) was added to the aqueous mixture causing a brown solid to precipitate. The solid was separated, and the H2O content of the filtrate increased by 10 mL until no more precipitate was observed. The collected solids were then triturated in CH3OH (25 mL) and cooled to -20 °C for two weeks. The Cl -complex of the desired product was separated and dried. Anion exchange was then performed by suspending the solid in CH3CN (25 mL), KPF6 (10 equivs.) was added, and the mixture was stirred for 12 h. The fine mauve solid was then filtered and washed with H2O (excess) before being dried in vacuo, with a final yield of 0.00552 g (<1%). 5-Fluoro-N 1 ,N 3 -diphenylisophthalamide (Isophthalamide 5) 5-Fluoroisophthaloyl dichloride (0.60192 g) was prepared using a previously reported method, which was then dissolved in CH2Cl2 and stirred while the system was purged with N2(g) for 10 min. Aniline (0.5703 mL, 0.55801 g, 2.2 equivs.) was added in slight excess dropwise over 30 s, where the solution turned translucent yellow to deep California brick red as a precipitate began to form. The reaction was allowed to stir for 2.5 h at r.t. after which the precipitate was filtered, and the light-creamcoloured solid was washed with CH2Cl2 (3×10 mL) and n-hexane (excess). The solid was then resuspended in CHCl3 (60 mL) and washed with H2O (3×60 mL) before HCl (1 M, 1 mL) was added to the aqueous phase of the third wash. The organic phase was collected and dried over MgSO4 (Anhyd.) before filtration and evaporation under reduced pressure. The white solid was dried for 12 h in vacuo, resulting in the isolation of 5 with a final yield of 0.46285 g (51%). Benzamide 6 was synthesised according to previously reported methods. First dissolving ortho-phenylenediamine (1.0039 g) in CH2Cl2 (50 mL). The reaction mixture was cooled to 0 °C over an ice bath. Dropwise addition of 3-fluorobenzoyl chloride (2.26 mL, ~2 equivs.) to the reaction mixture over 5 min resulted in an immediate bubbling exothermic reaction as HCl(g) was generated while the desired product began to precipitate as a light pink solid (which was quite aromatic and smelt like bananas when filtered later in the reaction). As the reaction progressed, it was especially important to ensure that outgassing could easily occur to reduce any built-up system pressure. After 2.5 h, the precipitate was separated, washed with CH2Cl2 (0 °C, 2×10 mL) and H2O (2×10 mL), and dried in vacuo for 12 h. The desired product was isolated as a white solid with a final yield of 1.0894 g (33%).