Self-Assembly of Octanuclear PtII/PdII Coordination Barrels and Uncommon Structural Isomerization of a Photochromic Guest in Molecular Space.

Abstract

Two tetragonal molecular barrels TB1 and TB2 were successfully synthesized by coordination-driven self-assembly of a tetrapyridyl donor (L) of the thiazolo[5,4-d]thiazole backbone with cis-blocked 90° Pd(II) and Pt(II) acceptors, respectively. The single-crystal structure analysis of TB1 revealed the formation of a two-face opened tetragonal Pd8 molecular barrel architecture. In contrast, the isostructural Pt(II) barrel (TB2) is water-soluble. The large confined hydrophobic molecular cavity including wide open windows and good water solubility of the barrel TB2 made it a potential molecular container for the encapsulation of guests with different sizes and properties. This has been exploited to encapsulate and stabilize the open form of a photochromic molecule (G2) in water, while the same photochromic molecule exists exclusively in a cyclic zwitterionic form in aqueous medium in the absence of the barrel TB2. This cyclic form is very stable in water and does not go back to its parent open form under common external stimuli. Surprisingly, reverse switching of the cyclic form to a colored hydrophobic open form was also possible instantly in water upon addition of the solid barrel TB2 into an aqueous solution of G2. Such a fast reverse isomerization of an irreversible process in aqueous medium by utilizing host–guest interaction of the barrel TB2 and the guest G2 is interesting. The barrel TB2 was also capable of encapsulating the water-insoluble radical initiator G1 in aqueous medium.