Sensing of the Induced Helical Chirality by the Chiroptical Response of the Ferrocene Chromophore. Issue 2 (23rd December 2021)

• Record Type: Journal Article
• Authors: Nuskol, Marko; Šutalo, Petar; Kodrin, Ivan; Semenčić, Mojca Čakić
• Is Part Of: European journal of inorganic chemistry. Volume 2022:Issue 2(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2021-12-23
• Subjects: Circular Dichroism (CD) -- Chirality -- Density Functional Theory (DFT) -- Ferrocene -- Hydrogen bonds; Chemistry, Inorganic -- Periodicals; Organometallic chemistry -- Periodicals; Bioinorganic chemistry -- Periodicals; Solid state chemistry -- Periodicals; 546
• DOI: 10.1002/ejic.202100880
• Languages: English
• ISSNs: 1434-1948

Abstract

Abstract: The experimental (infrared, nuclear magnetic resonance, circular dichroism) and computational (density functional theory) methods allowed us to demonstrate the potential of the ferrocene chromophore to translate chiral information stored at N ‐terminally attached l ‐Ala, and transmitted through achiral (Aib) n sequence ( n =1 to 3), into a characteristic signal in circular dichroism spectra near 470 nm. The sufficiently long tetrapeptide forms a robust and highly organized 310 helices capable of perturbing the environment of the highly symmetric ferrocene chromophore in an asymmetric manner. The origin of the sign in the circular dichroism spectra of the ferrocene chromophore (near the 470 nm) strongly correlates with the sign of the dihedral angle χ, accounting for a rotation of a substituent attached to the cyclopentadienyl ring that depends on the helicity of peptide sequence. These observations may help us in the design of future ferrocene‐based probes for the assignment of the screw‐sense preference of short peptides. Abstract : Experimental and computational study of Boc−(Aib) n ‐NH−Fc and Boc‐l ‐Ala−(Aib) n ‐NH−Fc ( n =1–3) derivatives revealed the transfer of a chiral information from the l ‐Ala amino acid through the highly organized (Aib)3 sequence to a ferrocene core, which is easily detectable in CD spectra near the absorption maximum of the ferrocene chromophore.