We present the successful fabrication of POM-based hydrogels through the host–guest interactions between the inclusion complex of Anderson–adamantane and 6-acrylamido-β-CD.

Intramolecular charge transfers between π‐conjugated molecules and polyoxometalate (POM) clusters have been observed in donor–acceptor systems based on organic donors and inorganic POM acceptors, which unfortunately results in a general quenching of the chromophore luminescence. The development of POM–chromophore dyads that are capable of tackling the quenching process and enhancing the fluorescence intensity of such systems remains a highly challenging area of study. A family of organic–inorganic polyoxometalate hybrids, {[(n‐C4H9)4N]3[(MnMo6O24){(CH2)3CR}2]} [1, R = –NHCH2C14H9, namely (anthracen‐9‐ylmethyl)amino; 2, R = –NHCH2C13H9, (9H‐fluoren‐2‐ylmethyl)amino; 3, R = –NHCH2C10H7, (naphthalen‐2‐ylmethyl)amino; 4, R = –NHCH2C16H9, (pyren‐2‐ylmethyl)amino], were synthesized by covalently tethering π‐conjugated molecules onto an Anderson cluster. The resulting POM–chromophore dyads were fully characterized by various spectroscopic techniques, single‐crystal X‐ray diffraction analysis and ESI–MS. The fluorescence features of these dyads were studied in detail to verify a dramatic emission enhancement that can be achieved by fine‐tuning the microenvironment in solution and suppressing the intrinsic photo‐induced electron‐transfer process.