In Situ Conversion of Ligand to a Coordination Polymer via a Core@Shell Crystal: A Multi-Step Phase-Dependent Structural Transformation.

Two pseudopolymorphic 1D coordination polymers of the formulas [Cd(3,3'-pytz)(CH 3 OH) 2 (ClO 4 ) 2 ] n ( 1 ) and [Cd(3,3'-pytz)(CH 3 CN) 2 (ClO 4 ) 2 ] n ( 2 ) have been prepared using the electron-deficient 3,6-bis(pyridin-3-yl)-1,2,4,5-tetrazine (3,3'-pytz) ligand and cadmium perchlorate in the chloroform/methanol and chloroform/acetonitrile solvent system, respectively. It was observed that compounds 1 and 2 experienced one-step (CP reagent → CP product ) single-crystal-to-powder structural transformation to the pure water-coordinated compound [Cd(3,3'-pytz)(H 2 O) 2 (ClO 4 ) 2 ] n ( 3 ) by absorbing water vapor from air (solid-gas phase transformation). Interestingly, compounds 1 , 2 , and 3 undergo a different transformation path and show an in situ unique three-step (CP reagent → CP product → Ligand intermediate → CP product ) single-crystal-to-single-crystal (SCSC) structural transformation process through soaking in deionized water (solid-liquid phase transformation). In this fascinating transformation, we report for the first time the direct conversion of a ligand into a coordination polymer by a rare core-shell pathway in a solid-liquid phase transformation. In this process, we obtained compound {[Cd(3,3'-pytz)(H 2 O) 4 ](3,3'-pytz) 2 (ClO 4 ) 2 (H 2 O) 6 } n ( 4 ) (single-crystal = S , crystal = C , or microcrystal = P ) as mixed compounds of core-shell L@4C and 4S or core-shell L@4P and 4P for compounds ( 1 and 2 ) and 3 , respectively.