Self-assembled metallasupramolecular cages towards light harvesting systems for oxidative cyclization

Abstract

Synthesis of Pt(ii) based metallacages as aggregation induced emissive supramolecular architectures for fabricating artificial light harvesting systems for cross coupling cyclization under visible light is achieved.

Artificial Light‐Harvesting Systems Based on AIEgen‐branched Rotaxane Dendrimers for Efficient Photocatalysis

“…And for TG2 and TG3 , the values were from 1.68 ns to 0.91 ns and 1.72 ns to 0.91 ns, respectively. More importantly, according to the ratios of fluorescence intensities of TPE units for rotaxane dendrimers, the energy‐transfer efficiencies ( Φ ET ) were calculated to be 42.5 % for TG1‐ESY , 68.2 % for TG2‐ESY , and 71.6 % for TG3‐ESY , respectively (Figures S57–S59), which are relatively high compared with the previously‐reported supramolecular light‐harvesting systems [19b–f] …”

Artificial Light‐Harvesting Systems Based on AIEgen‐branched Rotaxane Dendrimers for Efficient Photocatalysis

“…And for TG2 and TG3 , the values were from 1.68 ns to 0.91 ns and 1.72 ns to 0.91 ns, respectively. More importantly, according to the ratios of fluorescence intensities of TPE units for rotaxane dendrimers, the energy‐transfer efficiencies ( Φ ET ) were calculated to be 42.5 % for TG1‐ESY , 68.2 % for TG2‐ESY , and 71.6 % for TG3‐ESY , respectively (Figures S57–S59), which are relatively high compared with the previously‐reported supramolecular light‐harvesting systems [19b–f] …”

Heteroleptic metallosupramolecular aggregates/complexation for supramolecular catalysis

“…Mukherjee and co-workers have developed supramolecular architectures containing tetraphenylethene (TPE) units which act as an aggregation-induced emissive (AIE) fluorophore [ 65 ]. The newly designed TPE-based tetraimidazole donor 19 has been treated with 180°/120° trans -Pt(II) acceptors which led to the coordination-driven self-assembly of 3D discrete molecular cages in aqueous medium ( Figure 5 ).…”

“…The 180° acceptor without an organic spacer, trans -[Pt(PEt 3 ) 2 (ONO 2 ) 2 ] 20 , provided the cage 23a with the molecular composition ( 20 ) 4 ( 19 ) 2 (NO 3 ) 8 , whereas 21 (with a spacer unit) led to the formation of the Pt 8 cage 24a = ( 21 ) 4 ( 19 ) 2 (NO 3 ) 8 . In a similar fashion the bent 120° acceptor 22 also assembled into the Pt 8 cage 25a = ( 22 ) 4 ( 19 ) 2 (NO 3 ) 8 [ 65 ]. Counter anion exchange from NO 3 − to PF 6 − made the cages soluble in acetonitrile.…”

“… Construction of artificial LHS using rhodamine B as an acceptor and 24b as donor generating a photocatalyst. Figure was adapted from [ 65 ]. (Published by the Royal Society of Chemistry, “Self-assembled metallasupramolecular cages towards light harvesting systems for oxidative cyclization“, © 2021 A. Kumar et al, distributed under the terms of the Creative Commons Attribution 3.0 Unported License, https://creativecommons.org/licenses/by/3.0).…”