Enantiopure Double ortho-Oligophenylethynylene-Based Helical Structures with Circularly Polarized Luminescence Activity

Year: 2022

Authors: Reinè P., Ortuso AM., Resa S., De Cienfuegos LA., Ribagorda M., Mota AJ., Abbate S., Longhi G., Miguel D., Cuerva JM.

Autors Affiliation: Univ Granada, Fac Sci, Unidad Excelencia Quim, Dept Organ Chem, Granada 18071, Spain; Univ Autonoma Madrid, Dept Organ Chem, Organ Chem Dept, C Francisco Tomas y Valiente 7, Madrid 28049, Spain; Univ Granada, Fac Sci, Unidad Excelencia Quim, Dept Inorgan Chem, Granada 18071, Spain; Univ Brescia, Inst Nazl Ott CNR, Brescia Res Unit, Dept Mol & Translat Med, Via Branze 45, I-25123 Brescia, Italy; Univ Granada, Unidad Excelencia Quim, Phys Chem Dept, Fac Pharm, Granada 18071, Spain.

Abstract: In this paper, we describe the optical and chiroptical properties of an enantiopure multipodal ortho-oligophenylethynylene (S,S,S,S)-1 presenting four chiral sulfoxide groups at the extremes. The presence of these groups together with alkynes allows the coordination with carbophilic Ag(I), and/or oxophilic Zn(II) cations, yielding double helical structures in an enantiopure way. In this sense, different behaviors in absorption, fluorescence, ECD and CPL spectra have been found depending on the stoichiometry and nature of the metal. We have observed that Zn(II) coordination favors an intensity increase of the electronic circular dichroism (ECD) spectra of compound (S,S,S,S)-1 yielding an M-helicity in the ortho-oligophenylene ethynylene (o-OPE) backbone. On the other hand, ECD spectra of final Ag(I) complex shows two different bands with an opposite sign to the free ligand, thus giving the P-helical isomer. In addition, circularly polarized luminescence (CPL) exhibit an enhanced intensity and negative sign in both complexes. Computational studies were also carried out, supporting the experimental results.

Journal/Review: CHEMPHOTOCHEM

Volume: 6 (1)      Pages from:   to:

More Information: We thank the Ministerio de Economia y Competitividad (CTQ2017-85454-C2-1-P and CTQ2017-85454-C2-2-P), Ministerio de Ciencia e Innovacion (PID2020-113059GB-C21 and PID2020-113059GB-C22) and Junta de Andalucia (P20.00162) (Spain) for funding and P.R. and A. O. G. also for FPU contracts. Funding for open access charge is acknowledged to Universidad de Granada / CBUA.We also thank Big&Open Data Innovation Laboratory (BODaI-Lab), University of Brescia, granted by Fondazione Cariplo and Regione Lombardia, for access to resources of Computing Center CINECA (Bologna), Italy. Support from the Italian MIUR (Grant No. 2017A4XRCA) is also acknowledged.
KeyWords: chiroptical properties; circularly polarized luminescence; foldamers; helical structures; supramolecular metallofoldamers
DOI: 10.1002/cptc.202100160

Citations: 4
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