Abstract
New luminescent PtII complexes with the chiral counter anions [PtCl(tpy)](l‐Hta) (1‐L) and [PtCl(tpy)](dl‐Hta) (1‐DL; tpy = 2,2′:6′,2′′‐terpyridine; l‐H2ta = l‐tartaric acid; dl‐H2ta = racemic tartaric acid) were synthesized and their vapochromic behavior was evaluated. Single crystal X‐ray analysis revealed that the stacked square‐planar PtII molecules in anhydrous 1‐DL formed a one‐dimensional columnar structure with weak intermolecular Pt···Pt interactions, while in anhydrous 1‐L the PtII molecules were dimerized with Pt···Pt interactions to form a zig‐zag stacked column. These differences were attributed to the different hydrogen bonding in the dl‐ and l‐Hta– ions. The dihydrates of 1‐DL and 1‐L displayed near‐identical crystal structures with comparable emission spectra derived from 3π–π* ligand emission. Both dihydrates exhibited MeOH‐vapor‐induced dehydration to form the anhydrous complexes. These presented broad 3MMLCT emission (549 and 565 nm, respectively), affected by the degree of intermolecular Pt···Pt interactions.
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