Insights into a New Multi‐Stimuli‐Responsive Photochromic Metal‐Organic Framework: Highly Sensitive Turn‐On Luminescence in a Lanthanum Phosphonate

Abstract The new microporous metal organic framework [La 2 (H 2 O) 5 (H 2 TPPE)]·3H 2 O ( CAU‐54 ), is obtained in a hydrothermal reaction of the linker 1,1,2,2‐tetrakis(4′‐phosphonophenyl)ethylene (H 8 TPPE) and La 3+ ions. The extensive characterization including temperature‐dependent crystal structures and spectroscopic properties allowed to understand the unique, multi‐responsive material properties. CAU‐54 exhibits rarely observed reversible photochromism as well as turn‐on photoluminescence by various external chemical or physical stimuli including change of pressure, solvent exchange, and temperature variation. These properties can be unequivocally assigned to the presence of tetraphenylethylene (TPE) moieties of the linker molecules within the MOF, i.e., the ordered spatial arrangement of the linker molecules, the presence of accessible pores as well as the coordination flexibility of the phosphonate groups and the rotational freedom of the linker. By temperature‐dependent steady‐state and time‐resolved luminescence studies, it is shown that this compound exhibits a) blue fluorescence that becomes effectively quenched at room temperature, b) green efficient luminescence with thermal stability up to 400 K, and c) red phosphorescence correlated to the observed photochromism. In addition, CAU‐54 shows unusual thermal expansion properties as shown by temperature‐dependent powder X‐ray diffraction measurements with identified transition points that correlate with the observed temperature‐dependent changes in the photoluminescence.