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Chromeazurol B (Na 2 HL) is a pH-sensitive (halochromic) dye based on a hydroxytriarylmethane core and two carboxylate functional groups, which makes it suitable for the synthesis of coordination polymers. Two new coordination polymers [NaZn 4 (H 2 O) 3 (L) 3 ]·3THF·3H 2 O (1) and [Zn 3 (H 2 O) 3 (μ 2 -OH 2 )(μ 3 -OH)(HL) 2 (H 2 L)]·2THF·3H 2 O (2) incorporating Chromeazurol B linkers have been prepared and characterised. The structure of 1 comprises pentanuclear heterometallic {Zn 4 Na} nodes linked by six L 3- anions to give a layered structure with a honeycomb topology. 2 crystallizes as a double-chain ribbon (ladder) structure with two types of metal node: a mononuclear Zn(ii) cation and tetranuclear {Zn(ii)} 4 cluster. Chromeazurol B anions link each tetranuclear cluster to four individual Zn(ii) cations and each Zn(ii) cation with four tetranuclear clusters. Both compounds show pH-sensitivity in water solution which can be observed visually, giving the first example of a halochromic coordination polymer. The halochromic properties of 1 towards HCl vapors were systematically investigated. As-synthesized violet-grey 1 reversibly changes color from orange to pink in the presence of vapors of 2 M and 7 M HCl, respectively. The coordination of the Chromeazurol B anion at each color stage was examined by diffuse reflectance spectroscopy and FT-IR measurements. The remarkable stability of 1 to acid and the observed reversible and reproducible color changes provide a new design for multifunctional sensor materials.

Halochromic coordination polymers based on a triarylmethane dye for reversible detection of acids