Understanding the interactions between the single components of hybrid systems is essential to drive the development of advanced functional materials. A prerequisite for this is the systematic variation of the building blocks of such compounds. Focusing on spiropyran@metal–organic framework (MOF) composite materials with noncovalently attached spiropyran dyes, both the host scaffold and the dye molecules can be systematically tuned. In this work, a broad substitution pattern was applied to systematically elucidate the characteristics of the resulting hybrid materials as a function of the supplemental substitution on spiropyran. The newly developed 12 composites exhibit substitution and host-dependent optical characteristics, which are particularly affected by the substitution of the 6′-position on the chromene ring. Through the favorable combination of the MOF host’s polarity and an adequate strength of the spiropyran’s indolinedonor–chromeneacceptor pair, reversible conversion between photoisomers is efficiently accomplished, especially for nitro-substituted spiropyrans inside MIL-68­(In).

Exploring synthesis methods fosters new ways to design materials in faster and cheaper ways. In this fundamental study, we present mechanochemical loading of photoactive dye molecules into porous metal-organic frameworks (= MOFs) as an alternative and promising strategy to form hybrid switch@-MOF systems. Six different spiropyrans were inserted into the two MOFs MOF-5 and MIL-68(In) in varying compositions. By this, the concentration-dependent enclosure characteristics were determined. This fast and simple synthesis strategy has never been reported so far, and thus provides completely new possibilities for the formation of two-or even multi-component systems.