Supramolecular Organic Frameworks of Brominated Bisphenol Derivatives with Organoamines

Abstract

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 2À ) 2 3 (HPZ(3), (TBBPF) 3 (HMTA) (4), (TBBPA) 3 (HMTA) (5), and (TBBPA) 3 3 (HMTA) 3 3 H 2 O (6) (PZ = piperazine; DABCO = diazabicyclo[2.2.2]octane; HMTA = hexamethylenetetramine). Compounds 1À6 were characterized by single-crystal and powder X-ray diffractions. The predominant driving forces in 1À6 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 2À }. 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 3 3 3 TBBPA 3 3 3 HMTA 3 3 3 TBBPA 3 3 3 HMTA 3 3 3 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 4À6 that exhibit 1D and 0D H-bonded supramolecular structures.

Dimethyl 5,5′-methylenebis(2-hydroxybenzoate)

“…For the preparation, see: Cushman & Kanamathareddy (1990); Mé ric et al (1993). For the structures of similar compounds, see: Lu et al (2011); Zhang et al (2009); Liu et al (2009). For graph-set analysis, see Etter et al (1990).…”

Unique Use of Dibromo–L–Tyrosine Ligand in Building of Cu(II) Coordination Polymer—Experimental and Theoretical Investigations

“…The C–OH and deprotonated C–O − groups were structurally characterized by single-crystal X-ray diffractions for brominated bisphenol derivatives (containing dibromo-4-hydroxyphenyl rings) with organoamines. It was found that the C-O − bond is much shorter (average value of 1.300 Å), while the C–OH bond (average value of 1.360 Å) [ 23 ] is similar to that for 1 .…”