Supramolecular Organic Frameworks of Brominated Bisphenol Derivatives with Organoamines

Reactions of two brominated bisphenol derivatives, tetrabromobisphenol-F (TBBPF) and tetrabromobisphenol-A (TBBPA), with various organoamines resulted in six supramolecular organic frameworks (SOFs), formulated as (TBBPF 2– ) 2 ·(HPZ + ) 2 ·(H 2 PZ 2+ ) ( 1 ), (TBBPF – ) 2 ·(H 2 PZ 2+ )·2H 2 O·2MeOH ( 2 ), (TBBPF)·(TBBPF – )·(HDABCO + )·H 2 O ( 3 ), (TBBPF)·(HMTA) ( 4 ), (TBBPA)·(HMTA) ( 5 ), and (TBBPA) 3 ·(HMTA) 3 ·H 2 O ( 6 ) (PZ = piperazine; DABCO = diazabicyclo[2.2.2]octane; HMTA = hexamethylenetetramine). Compounds 1 – 6 were characterized by single-crystal and powder X-ray diffractions. The predominant driving forces in 1 – 6 are hydrogen bonds (H-bonds), by which the compounds assemble into supramolecular organic frameworks with versatile topological structures. Compound 1 contains TBBPF/PZ in a 2:3 ratio and exhibits 2D (two-dimensional) H-bonded supramolecular 4 4 - sql layer structure built by the four-connected {H 2 PZ 2+ } moieties and {TBBPF 2– }. Compound 2 shows a 2-fold interpenetrated 3D (three-dimensional) H-bonded networks comprised by TBBPF/PZ in 2:1 ratio with the presence of solvent H 2 O and MeOH molecules, in which two identical pcu topological nets are recognized by choosing a decamer synthons as nodes. Compound 3 displays H-bonded 4 4 - sql layer structure built by 2:1 TBBPF and DABCO, as well as one H 2 O per formula unit. Compounds 4 and 5 assemble into 1D (one-dimensional) H-bonded zigzag chains via the alternate linkage of HMTA with TBBPF/TBBPA in a similar fashion. Compound 6 generates an interesting hexamer subunit (HMTA···TBBPA···HMTA···TBBPA···HMTA···TBBPA), which can be viewed as a fragment of three repeating units for a zigzag chain observed in compound 5 . A pair of the hexamer subunits is further connected by two water molecules to form an H-bonded molecular oligomer. Importantly, halogen bonds (X-bonds) have been observed in compounds 4 – 6 that exhibit 1D and 0D H-bonded supramolecular structures.