Assembling of a Water-Soluble N^C^N-Coordinated Pt(II) Complex Aggregate Assisted by Carbon Dioxide in Basic Aqueous...

We report an unprecedented result of self-aggregation of [Pt(L¹ )Cl] (HL¹ =1,3-di(5-carboxy-2-pyridyl)benzene) triggered by CO₂ in basic aqueous solution. The color of basic aqueous solution containing [Pt(L¹ )Cl] changes from yellow to blue-green during the aggregation resulted from a reaction with CO₂ in air. Upon CO₂ gas bubbling, strong and broad absorption bands of aggregate assigned to the metal-metal-to-ligand charge-transfer transition appeared at 701 and 1152 nm. Recrystallization of [Pt(L¹ )Cl] from Na₂ CO₃ aqueous solution afforded polymorphic crystals of red and blue-green forms. A single X-ray crystallography revealed that the red form of crystal consists of a Pt-Pt stacked dimer bridged by CO₃ ^2- ion and one of the carboxy groups of L¹ is deprotonated. An elemental analysis provided evidence that the blue-green crystal is constructed by linear array consisting of the [Pt(L² )(CO₃ )]^3- (HL² =1,3-di(5-carboxylate-2-pyridyl)benzene) units. The formation process of blue-green aggregate in aqueous solution was monitored through a transient absorption spectrum, and the absorption of aggregates involved in the spectral change were examined by a global analysis. A singular value decomposition and kinetic analysis provide that there are four species resulted from the self-assembling reaction in the solution and the maximal degree of aggregation is at least 32-mer.