Direct Integration of Red‐NIR Emissive Ceramic‐like A_nM₆Xⁱ₈X^a₆ Metal Cluster Salts in Organic Copolymers Using Supramolecular Interactions

Abstract

Hybrid nanomaterials made of inorganic nanocomponents dispersed in an organic host raise an increasing interest as low-cost solution-processable functional materials. However, preventing phase segregation while allowing a high inorganic doping content remains a major challenge, and usual methods require a functionalization step prior integration. Herein, we report a new approach to design such nanocomposite in which ceramic-like metallic nanocluster compounds are embedded at 10 wt % in organic copolymers, without any functionalization. Dispersion homogeneity and stability are ensured by weak interactions occurring between the copolymer lateral chains and the nanocluster compound. Hybrids could be ink-jet printed and casted on a blue LED. This proof-of-concept device emits in the red-NIR area and generates singlet oxygen, O ( Δg), of particular interest for lights, display, sensors or photodynamic based therapy applications.

PLGA nanoparticles embedding molybdenum cluster salts: Influence of chemical composition on physico-chemical properties, encapsulation efficiencies, colloidal stabilities and in vitro release

“…EE%, CL and MY% for all CNPs with 3 different P/C ratios (each value is the mean ± SD of 3 determinations). : values obtained previously in our team (same experimental conditions and apparatus) by Amela-Cortes (2014), Robin (2018) and Nayak (2015), respectively.…”

“…This phenomenon is a totally reversible physical phenomenon that does not lead to a chemical alteration of the emitting cluster, as seen with the lack of emission maximum shift. Incorporation of molybdenum clusters in polymeric PLGA network led to a decrease of AQY (Table 4) and this was also reported with several cluster compounds, ((C 4 H 9 ) 4 N) 2 (Mo 6 I 8 )(NO 3 ) 6 ) , ((C 4 H 9 ) 4 N) 2 {Mo 6 I 8 }(CF 3 CO 2 ) 6 ) (Kirakci et al, 2012) and CMB (Aubert et al, 2013;Grasset et al, 2008) following their incorporation into SiO 2 micro or nanoparticles and was also reported for Mo 6 clusters after incorporation in PMMA (Amela- Cortes et al, 2016) or PMMA-PEOMA copolymer (Robin et al, 2018) matrixes, these modifications being attributed to perturbation of the ligand environment in the polymeric matrix or to cluster compound instability during nanoparticles preparation, i.e. apical ligand substitution by water molecules.…”

Switchable Two-Dimensional Waveguiding Abilities of Luminescent Hybrid Nanocomposites for Active Solar Concentrators

“…38 Hence, the Cs2Mo6I8(OCOC2F5)6 triplet state lifetime decreases from 269 µs for a fully deaerated acetone solution to 2 µs for an aerated one. 39 The same trend is observed Figure S5). The emissive O2 ( 1 g) singlet oxygen is generated by reaction of the cluster triplet excited state with the triplet oxygen O2 ( 3 g -) contained in the atmosphere which is in good accordance with the shortening of its emission lifetime.…”

Ionic columnar clustomesogens: associations between anionic hexanuclear rhenium clusters and liquid crystalline triphenylene tethered imidazoliums

“…[29][30][31][32][33][34][35] Because of their high potential in biology for ROS production, as nanoscintillators or contrast agents, [36][37][38] in optoelectronic [39][40][41] or lighting, 42 many efforts have been devoted these last years to counterpart their ceramic-like behaviour and integrate them in host matrices. [43][44][45][46][47][48][49][50][51][52][53][54] Hence, several strategies have been developed to solubilize the [M 6 Q i 8 X a 6 ] nanionic units in organic media, 55,56 or to integrate them directly in a polymeric or liquid crystalline organic host matrix 23,25,49,57,58 by replacing, via a metathesis reaction, their alkali counter cations by functional organic ones. Nonetheless, combining isometric transition metal clusters and rod-like mesogens through the ionic self-assembly approach leads only to nematic or lamellar liquid crystalline phases.…”