Emission-Tunable Soft Porous Organic Crystal Based on Squaraine for Single-Crystal Analysis of Guest-Induced Gate-Opening Transformation

Soft porous crystals (SPCs) with both crystallinity and flexibility have evolved as emerging materials for lots of applications. However, the development of purely organic SPCs (SPOCs) with advanced functionalities significantly lags behind. Herein, we report the construction of an emission-tunable SPOC with a rationally designed squaraine derivative (named as SPOC-SQ). SPOC-SQ is featured with a squaraine core and four peripheries with electron donor-π-acceptor (D-π-A) characteristics, which facilitates the formation of porous crystal framework stabilized by π-π interactions and H bonds and at the same time provides structural flexibility through phenyl rotations. This SPOC can be easily obtained from its dichloromethane (DCM) solution and exhibits reversible stimuli-responsive single-crystal-to-single-crystal (SCSC) structural transformation, accompanied by bright and tunable emission. In addition, this activated SPOC (SPOC-SQ-a) selectively recognizes and absorbs acetylene (C₂H₂) over other gases without destroying the single crystallinity, enabling the single-crystal XRD analysis of the structural transformation. Close inspection of single-crystal XRD results of SPOC-SQ-C₂H₂ facilitates the understanding of the host-guest interactions. More interestingly, upon interacting with C₂H₂, a one-dimensional (1D) channel is formed in the crystal to adopt C₂H₂, which proves the SCSC process and provides molecular-level insights into the gate-opening process. Furthermore, C₂H₂ adsorption dynamics can be monitored in real time by tracking the fluorescence wavelength changes of SPOC-SQ framework. Thus, the unique gate-opening sorption attribute of SPOC-SQ-a crystals toward C₂H₂ enables its potential applications for gas separation.