Luminescent Supramolecular Ionic Frameworks based on Organic Fluorescent Polycations and Polyanionic Phosphorescent Metal Clusters

Abstract

Emissive ionic supramolecular frameworks are obtained by associating a tetraphenylethylene‐based tetra‐cationic units and di‐anionic molybdenum or tetra‐anionic rhenium octahedral clusters. Obtained structures were characterized by single‐crystal X‐ray diffraction. The emission properties of the hybrids were investigated as dry powders or in various solvents by one photon and two photon absorption leading to a O2 concentration dependent luminescence color for the Mo based hybrid.

Smart emissive hybrid dynamer and nanocomposite made of complementary organic and inorganic emitters combined via a supramolecular Janus synthon

“…The mechanism of the colour changes, and thus the writing process, is attributed to the increase of the cluster compound emission efficiency induced by a depletion of the local O 2 concentration within the PMMA film upon irradiation. We already observed such a phenomenon when [Mo 6 I 8 (OCOC 2 F 5 ) 6 ] 2− was associated with oxindole 53 or tetraphenylethylene 54 derivatives. In fact, the O 2 concentration lowering is induced by the reaction of the fundamental O 2 ( 3 Σ g − ) triplet state with the cluster compound excited triplet state.…”

Supramolecular Systems Linked to Metal‐Organic Frameworks

“…This approach focuses on octahedral metallic cluster of general formula An[M6L i 8L a 6] (A = alkali cation, M = transition metal; L i = inner ligand; L a = apical ligand). The metallic scaffold M6 is covalently bonded to face-capping ligands (μ3-L i ) and is stabilized by six apical ligand L a [54].…”

Emissive supramolecular ionic crystals combining a red-NIR phosphorescent [Re6Se8CN6]4− cluster anion and a blue fluorescent tetraphenylethene counter-cation

“…Combining them with a non-emissive bisamidinium cation leads to a red NIR emissive network in which the stabilization was mainly driven by H-bonds, 28 while using a tetra-cationic TPE drove the formation of an insoluble red emissive extended network maintained by electrostatic interactions. 29 Usually, emissive materials containing several dyes are able to deliver efficiently a tailored emission that depends on the dye concentration and ratio. However, the degree of interactions between the emitters should also be considered to adjust the emission response toward the applied stimulus.…”

“…Herein, by lowering the cationic charge on the TPE unit, we expected a higher contribution of the TPE signal to the global emission envelope, compared to previously reported data. 29 Here, we present the first supramolecular ionic framework based on a di-cationic TPE and a tetra-anionic octahedral rhenium cluster complex.…”