Thymine functionalised porphyrins, synthesis and heteromolecular surface-based self-assembly† †Electronic supplementary information (ESI) available: Additional experimental details including: full synthetic methods and characterization; full details of single crystal X-ray structure refinement and CIFs; binding measurements; STM experiments; and MM simulations. CCDC 1034260 and 1034261. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c4sc03531c Click here for additional data file. Click here for additional data file.

3,5-di-tert-butylphenyl morpholin-4-yl ketone. 3,5-di-tert-butylbenzoic acid (7 g, 29.9 mmol) was added to a flame dried flask which had been backfilled with nitrogen three times. DCM (70 mL) was added via canula, followed by DMF (0.77 mL, 9.9 mmol) and oxalyl chloride (2.3 mL, 26.9 mmol) added dropwise over 15 minutes. The mixture was stirred at room temperature for 1 h 30 under a nitrogen atmosphere. In a second flame dried, backfilled flask, morpholine (9.3 mL, 108 mmol) and triethylamine (4.3 mL, 30.8 mmol) was added to DCM (70 mL). This mixture was added to the first flask slowly via canula over 20 minutes. The solution was stirred at room temperature for 2 h under a nitrogen atmosphere. The mixture was then quenched with 0.5 M HCl (100 mL) and stirred for 30 minutes at room temperature. The organic layer was then separated, washed with water (3 × 100 mL), dried over MgSO4 and evaporated under reduced pressure to yield pure compound (8.98 g, 99 %). MS (EI): m/z Calc = 304.2271 (M + H); Found = 304.2262 (M + H), 326.2061 (M + Na). H NMR (CDCl3, 400 MHz): δH = 7.50 (t, J = 1.8 Hz, 1H), 7.25 (d, J = 1.8 Hz, 2H), 3.85 – 3.40 (m, 8H), 1.35 (s, 18 H). C NMR (101 MHz, CDCl3) δC = ppm 171.37 (s, 1 C) 151.04 (s, 2 C) 134.56 (s, 1 C) 123.81 (s, 1 C) 121.18 (s, 2 C) 66.86 (s, 2 C) 53.44 (s, 2 C) 34.88 (s, 2 C) 31.35 (s, 6 C). Anal. Calcd for C19H29NO2: C, 75.21; H, 9.63; N, 4.62. Found: C, 75.36; H, 9.74; N, 4.65.