Strongly Hydrogen-Bonded Networks Formed by Sulfate and Bisulfate Salts of Benzenetetramines

Abstract

Benzenetetramines, like other aromatic compounds with multiple NH2 groups, are easily oxidized and are attractive candidates for use as components of redox-active organic materials. However, many aspects of the chemistry of benzenetetramines and related compounds remain poorly understood, such as the nature of their salts and their preferred patterns of association, which determine how they can be used to construct predictably ordered redox-active solids. To provide relevant new information, we have studied a series of sulfate and bisulfate salts of the 1,2,4,5- and 1,2,3,4-isomers, which have been found to crystallize as strongly hydrogen-bonded networks. The results of this work promise to facilitate the use of benzenetetramines and other complex arylamines as components of redox-active organic solids.

Refreshing the Legacy of Rudolf Nietzki: Benzene-1,2,4,5-tetramine and Related Compounds

“…The resulting precipitate was separated by filtration, washed with cold EtOH, and dried in a vacuum to give the sulfate salt of benzene-1,2,3,4-tetramine ( 7 ·H 2 SO 4 ) as a crystalline solid (0.72 g, 3.0 mmol, 37% overall yield): 1 H NMR (400 MHz, D 2 O containing added DCl to increase solubility) δ 6.78 (s, 2H); 13 C­{ 1 H} NMR (101 MHz, D 2 O) δ 126.5, 121.3, 117.7. The structure of the product was confirmed by single-crystal X-ray diffraction …”

Supramolecular design as a route to high-performing organic electrodes

“…For example, Wuest and coworkers demonstrated how various redox-active benzene tetramine isomers crystalize. 52 They found that they could direct the resultant crystalline structure of these salts by engineering the H-bonding environment. Later, Wuest and coworkers showed how more complex benzoquinone-hydroquinone cocrystals could be generated by synergistic hydrogen bonds between these redox-active units.…”

Synthesis and structural trends in a series of simple tetraalkylphosphonium salts

“…In fact, the HSO 4 − anion may serve the latter role well – several organic and inorganic sulfate-hydrogen sulfate mixed-anion systems have been reported with strong (SO 4 ⋯HSO 4 ) 3− hydrogen bonds (O⋯O <2.5 Å, H⋯H ≪1.5 Å). 23–26…”