Supramolecular Structure in s‐Block Metal Complexes of Sulfonated Monoazo Dyes: Discrepant Packing and Bonding Behavior of ortho‐Sulfonated Azo Dyes

Abstract

The first solid-state structures of ortho-sulfonated monoazo dyestuffs are reported and compared to those of their para- and meta-sulfonated analogues. The structures of the 16 Na, K, Cs, Mg, Ca, Sr, and Ba ortho-sulfonated salts are found to have fewer M-O(3)S bonds than their isomeric equivalents and this in turn means that the metal type is no longer the prime indicator of which structural type will be adopted. M-O(3)S bonds are replaced by M-OH(2), M-HOR and M-pi interactions, apparently for steric reasons. As well as new bonding motifs, the changed dye shape also leads to new packing motifs. The simple organic/inorganic layering ubiquitous to the para- and meta-sulfonated dye salt structures is replaced by variations (organic bilayers, inorganic channels), each of which correlates with a different degree of molecular planarity in the sulfonated azo dye anion.

Influence of Metal Cations and Coordination Modes on Luminescent Group 1 and 2 Metal Sulfonate Complexes Constructed from 4,4′‐Dihydroxybiphenyl‐3,3′‐disulfonic Acid

“…[13] Five years later, they reported another series of group 1 and 2 metal arenesulfonate coordination solids based on ortho-sulfonated monoazo dyes, in which the packing motifs correlate with the degree of molecular planarity in the sulfonated azo dye anions. [14] A Scheme 1. Schematic representation of the syntheses.…”

“…[12][13][14] In 2001, Cai and co-workers reported a family of group 1 and 2 metal arenesulfonates incorporating 1,5-naphthalenedisulfonic acid (1,5-H 2 NDS), and the structural evolution was influenced by the coordination modes of the 1,5-NDS 2-ligand. [12] In 2004, Kennedy et al presented a series of group 1 and 2 metal arenesulfonate salts based on para-and meta-sulfonated azo dyes.…”

Ag(i) bipyridyl coordination polymers containing functional anions

“…[9,10] The structures of the chosen counterion formers' salt forms and cocrystal forms have thus been widely studied. [11][12][13][14][15][16][17][18][19][20][21][22][23][24] We present these new structures both to investigate the structural effect of introducing large anions into Ag(I) bipyridyl structures and because including such counterions within coordination polymers opens up the possibility of dramatic changes to the chemicophysical properties of the counterion (e.g. aqueous solubility, dissolution rate and mechanical strength) and thus is a potential route to new and improved formulations.…”

Molecular Recognition of Two 2,4‐syn‐Functionalized (S)‐Glutamate Analogues by the Kainate Receptor GluK3 Ligand Binding Domain

“…Moreover, the sulfonate group is usually considered to be a weak ligand, as is often evidenced by its inability to replace water molecules from the primary coordination spheres of many metal ions; in many cases, it is only involved in hydrogen‐bonding supramolecular networks 1. Although some group 1 and 2 metal arenesulfonates have been reported,9 there are few systematic studies on the evolution of the structural features of group 1 and 2 metal arenesulfonates with respect to the nature of the metal cations and the coordination modes of the ligand 12–14. In 2001, Cai and co‐workers reported a family of group 1 and 2 metal arenesulfonates incorporating 1,5‐naphthalenedisulfonic acid (1,5‐H 2 NDS), and the structural evolution was influenced by the coordination modes of the 1,5‐NDS 2– ligand 12.…”

“…These salts form different structures, which are primarily governed by metal type but can also be influenced by the nature and position of the organic substituents 13. Five years later, they reported another series of group 1 and 2 metal arenesulfonate coordination solids based on ortho ‐sulfonated monoazo dyes, in which the packing motifs correlate with the degree of molecular planarity in the sulfonated azo dye anions 14. A close inspection of these cases reveals that the coordination modes of the sulfonate groups are simple, and this then leads to small changes to the structures.…”