Halogenated tennimides and trezimides: impact of halogen bonding and solvent role on porous network formation and inclusionElectronic supplementary information (ESI) available: The 1H, 13C NMR, high resolution MS and IR spectroscopic and single crystal data for all eight macrocycles are provided with CCDC reference codes 1062025-1062032, together with two additional deposited CIFs as (ClIO)4 solvents. CCDC reference codes 1062204 and 1062205. For ESI and crystallographic data in CIF or other ele

Fluorine and chlorine derived macrocycles ( FIO ) 3 / 4 and ( ClIO ) 3 / 4 are synthesised from the reaction of isophthaloyl dichloride with 2-amino-5-fluoropyridine and 2-amino-5-chloropyridine, respectively. Solvents of crystallisation are present in the six F/Cl crystal structures and occupy 12-43% of crystal lattice. Halogenated solvents (CH 2 Cl 2 ; CHCl 3 ) typically link macrocycles through halogen and hydrogen bonding interactions forming 1-D chains through halogen bonding, whereas dimethylsulfoxide (DMSO) incorporation promotes solvent channel formation. For ( ClIO ) 3 , the total (%) solvent comprising DMSO and water molecules is 43% of the structure volume with 3.5(DMSO)·3(H 2 O) per ( ClIO ) 3 macrocycle resulting in extensive channel formation. The solvent channel aggregation assists 2-D network formation in combination with short C-Cl O&z.dbd;C halogen bonding interactions and C-Cl Cl-C contacts (Cl O, Cl Cl; both N c = 0.90). Of further note is that ( ClIO ) 4 ·CH 2 Cl 2 is isomorphous with two methylated analogues ( MIO ) 4 ·CH 2 Cl 2 and ( MIO ) 4 ·CHCl 3 . The role of halogenated and aprotic solvents in macrocyclic structures is assessed in terms of halogen and hydrogen bonding interactions.