An atomically precise silver nanocluster for artificial light-harvesting system through supramolecular functionalization. Issue 28 (30th June 2022)

• Record Type: Journal Article
• Authors: Das, Anish Kumar; Biswas, Sourav; Manna, Surya Sekhar; Pathak, Biswarup; Mandal, Sukhendu
• Is Part Of: Chemical science. Volume 13:Issue 28(2022)
• Page Start: 8355
• Page End: 8364
• Publication Date: 2022-06-30
• Subjects: Chemistry -- Periodicals; 540.5
• DOI: 10.1039/d2sc02786k
• Languages: English
• ISSNs: 2041-6520

Abstract

Abstract : A β-cyclodextrin functionalized atomically precise Ag16 based artificial light-harvesting system is fabricated with 93% energy transfer efficiency from the blue to the green emission region of the acceptor β-carotene molecule. Abstract : Designing an artificial light-harvesting system (LHS) with high energy transfer efficiency has been a challenging task. Herein, we report an atom-precise silver nanocluster (Ag NC) as a unique platform to fabricate the artificial LHS. A facile one-pot synthesis of [Cl@Ag16 S(S-Adm)8 (CF3 COO)5 (DMF)3 (H2 O)2 ]·DMF (Ag16 ) NC by using a bulky adamantanethiolate ligand is portrayed here which, in turn, alleviates the issues related to the smaller NC core designed from a highly steric environment. The surface molecular motion of this NC extends the non-radiative relaxation rate which is strategically restricted by a recognition site-specific supramolecular adduct with β-cyclodextrin (β-CD) that results in the generation of a blue emission. This emission property is further controlled by the number of attached β-CD which eventually imposes more rigidity. The higher emission quantum yield and the larger emission lifetime relative to the lesser numbered β-CD conjugation signify Ag16 ∩ β-CD2 as a good LHS donor component. In the presence of an organic dye (β-carotene) as an energy acceptor, an LHS is fabricated here via the Förster resonance energy transfer pathway. The opposite charges on the surfaces and the matched electronic energy distribution result in a 93% energy transfer efficiency with a great antenna effect from the UV-to-visible region. Finally, the harvested energy is utilized successfully for efficient photocurrent generation with much-enhanced yields compared to the individual components. This fundamental investigation into highly-efficient energy transfer through atom-precise NC-based systems will inspire additional opportunities for designing new LHSs in the near future.