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Organosulfonates (RSO₃⁻) are largely regarded as poor ligands by coordination chemists, and have typically been employed as ‘non coordinating’ anions in past synthetic and structural work. Indeed, the majority of transition metal aqua complexes with sulfonate counter anions show that the sulfonate group cannot readily displace water from the coordination sphere of the metal ion. There exists a strong structural analogy between the RSO₃⁻ and the phosphonate RPO₃²⁻ group, a functionality which has been employed with great success in the generation of functional extended architectures. The contrast lies in the fact that individual metal–oxygen interactions with the sulfonate group are weaker, when employed with suitably soft metal cations, but may be employed cooperatively, to still yield a stable solid. This review deals with some of the functional frameworks we have reported which take advantage of the …