*2.2. Synthesis and Characterisation*

Synthesis of **H2L1**: A suspension of l-leucine (150 mg, 1.15 mmol) and 9,10-dimethyl-9,10-dihydro-2,3,6,7-tetracarboxyl-9,10-ethanoanthracene (190 mg, 0.463 mmol) was added to a round-bottomed flask with acetic acid (20 mL) and heated at 120 ◦C for four nights, during which time all solids were taken into solution. After this time the light-yellow solution was poured over ice, forming a light-yellow precipitate, which was recovered by filtration, washed with water and dried in vacuo. Yield: 172.5 mg, 62%. m.p. 195–198 ◦C. Found: C, 63.56; H, 5.96; N, 3.99%; C34H36N2O8. Requires: C, 63.32; H, 6.15; N, 3.89%. δH (400 MHz, *d*6–DMSO): 0.81 (m, 12H, CH2CH*Me*2); 1.36 (m, 2H, CH2C*H*Me2); 1.67 (s, 4H, C*H*2C*H*2); 1.8 (m, 2H, C*H*2CHMe2); 2.21 (s, 6H, Mecore); 2.16 (m, 2H, C*H*2CHMe2); 4.74 (dd, 3*J* = 12, 3*J* = 4.2 Hz, 2H, NC*H*); 7.78 (s, 4H, ArH). δC (100 MHz, *d*6–DMSO): 21.1; 23.5; 26.1; 37.1; 43.4; 44.3; 50.6; 116.6; 129.7; 152.8; 168.0; 171.3. <sup>υ</sup>max/cm<sup>−</sup>1: 2958w; 2871w; 1841w; 17,700m; 1702s; 1617m; 1534w; 1465w; 1442w; 1377s; 1321w; 1250m; 1205m; 1155m; 1088w; 991w; 911w; 869w; 752m. *m*/*z* (ES−): 504.1 ([M-Leu + OH]<sup>−</sup>, calculated for C26H26NO8<sup>−</sup>, 504.2), 100%; 599.2 ([M − H]<sup>−</sup>, calculated for C34H35N2O8<sup>−</sup>, 599.2) 93%.

Synthesis of **H2L2**: The synthesis was based on a literature report with minor modifications [52]. Pyromellitic dianhydride (0.707 g, 3.24 mmol) and l-alanine (0.752 g, 8.44 mmol) were added to a round-bottomed flask with acetic acid (40 mL) and heated under reflux overnight, giving a colourless solution. Concentrated hydrochloric acid (20 mL) was added to the solution, which was allowed to concentrate by evaporation overnight to give a white powder. The product was collected by vacuum filtration, washed with cold water, added dropwise, and dried in air. Yield: 0.703 g, 60%. δH (400 MHz, *d*6–DMSO): 1.59 (d, 6H, Me); 4.96 (q, 2H, NC*H*); 8.30 (s, 2H, ArH); 13.32 (s, 2H, CO2H). δC (100 MHz, *d*6–DMSO): 15.14; 48.02; 118.45; 137.26; 165.92; 171.14. <sup>υ</sup>max/cm<sup>−</sup>1: 3570w; 3146w; 3007w; 2953w; 1758w; 1702s; 1618w; 1561w; 1459m; 1383m; 1364m; 1304m; 1252w; 1208w; 1171w; 1154w; 1132w; 1104w; 1067m; 1018wm; 934m; 854m; 822w; 802w; 761w; 726m; 677w. *m*/*z* (ES−): 315.1 ([M-COO-H]<sup>−</sup>, calculated for C15H11N2O6<sup>−</sup>, 315.1) 100%; 359.1 ([M − H]<sup>−</sup>, calculated for C16H11N2O8<sup>−</sup>, 359.1) 20%.

Synthesis of [Cu4(**L1**)4(DMF)(OH2)3]·3.5DMF·9.5H2O (compound **1**): **H2L1** (10 mg, 16.7 μmol) and Cu2(OAc)4 (6.0 mg, 33.3 μmol) were added to DMF (1 mL) and sonicated to dissolve. The solution was heated at 85 ◦C for two nights during which time light blue/green block-shaped crystals formed, which were recovered by vacuum filtration. Yield: 2.2 mg, 61%. Found: C, 56.04; H, 5.58, N, 5.59%; C139H149N9O36Cu4·3.5DMF·9.5H2O ([Cu4(**L1**)4 (DMF) (OH2)3]·3.5DMF·9.5H2O). Requires: C, 56.14; H, 6.02; N, 5.31%. <sup>υ</sup>max/cm<sup>−</sup>1: 2955w; 2869w; 1771w; 1709 s; 1637m; 1465w; 1411m; 1377s; 1351m; 1259w; 1204w; 1156w; 1101w; 1062w; 992w; 913w; 870w; 805w; 771w; 755m; 729w; 660m. *m*/*z* (ES+): 2649.7 (cage + H)<sup>+</sup>, calculated for C136H136Cu4N8O32<sup>+</sup>, 2647.645; 2708.7 (cage + H2O + MeCN + H)<sup>+</sup>, calculated for C138H141Cu4N9O33<sup>+</sup>, 2706.683. TGA: On-set, 70 ◦C, mass loss = 10% (calculated 11.8% for loss of two non-coordinated H2O and 4.5 DMF molecules and all coordinated solvent); decomp, 350 ◦C.

Synthesis of [Co8(**L2**)8(DABCO)3(OH2)8]·solvent (compound **2**): **H2L2** (10 mg, 28 μmol), DABCO (1.6 mg, 14 μmol), and Co(NO3)2·6H2O (8.1 mg, 28 μmol) were added to DMF (2 mL) and sonicated to dissolve. The solution was heated at 100 ◦C for three nights during which time crystalline royal blue plates formed. Only one or two small single crystals formed, preventing bulk analysis. *m*/*z* (ES−): 955.9 ([Co4(**L2**)4(DABCO)(H2O)3(OH)]NO3)<sup>2</sup><sup>−</sup>, calculated for C70H59Co4N11O39<sup>2</sup><sup>−</sup>, 956.0; 1841.9 ([Co4(**L2**)4(DABCO)]NO3)-, calculated for C70H52Co4N11O35<sup>−</sup>, 1842.0.
