Anion–π Interaction‐Induced Room‐Temperature Phosphorescence of a Polyoxometalate‐Based Charge‐Transfer Hybrid Material.

Abstract: Room‐temperature phosphorescence (RTP) was realized for the first time in a polyoxometalate‐based charge‐transfer (CT) hybrid material bearing polyoxometalates (POMs) as electron‐donors (D) and rigid naphthalene diimides (NDIs) as electron‐acceptors (A), meanwhile, this hybrid material displayed photochromism as well. The significant D‐A anion–π interaction induced an additional through‐space charge‐transfer pathway. The resulting suitable D‐A CT states can efficiently bridge the relatively large energy gap between the NDI‐localized 1π–π* and 3π–π* states and thus trigger the ligand‐localized phosphorescence (3π–π*). [ABSTRACT FROM AUTHOR]