Co(<scp>ii</scp>)-induced giant vibrational CD provides a new design of methods for rapid and sensitive chirality recognition

Berardozzi, Roberto; Badetti, Elena; Santos, Nadia Alessandra Carmo dos; Wurst, Klaus; Licini, Giulia; Zonta, Cristiano; Bari, Lorenzo Di

doi:10.1039/c6cc04167a

Cited by 41 publications

(24 citation statements)

References 20 publications

(28 reference statements)

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“…[41][42][43][44][45] On a parallel track, in the recent years, we are assisting to a revival of interest in the well-known, and widely exploited in nature, imine condensation chemistry. 8,[52][53][54][55][56][57][58][59][60][61][62] In this study, we extend the sensing capabilities of our zinc TPMA-based stereodynamic probe, showing its efficiency towards chiral amines, acids, and β-amino acids. 46,47 However, the main reason of interest lies in the reversibility of the C═N bond formation, which is extremely useful in dynamic covalent chemistry (DCC) and in the synthesis of functional architectures, and it is particularly effective in the presence of transition metal complexes.…”

Section: Introductionmentioning

confidence: 72%

Extending substrate sensing capabilities of zinc tris(2‐pyridylmethyl)amine‐based stereodynamic probe

et al. 2019

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Tripodal metal complexes have been widely used for catalysis and more recently also for molecular recognition applications. Their ability in recognition and signal amplification of chiral substrates is because of the setup of the ligand around the metal in a propeller shape. Within this subject, we have recently reported tris(2-pyridylmethyl)amine-and triphenolamine-based complexes for the determination of the enantiomeric excess of various substrates.Herein, we show the versatility of the zinc tris(2-pyridylmethyl)amine-based stereodynamic probe by performing a detailed study of the imine formation process, by the extension of the sensing capabilities to other chiral compounds. A principal component analysis study of the system together with TD-DFT studies highlights the molecular origin of the observed chiroptical properties.

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Section: Introductionmentioning

confidence: 72%

Extending substrate sensing capabilities of zinc tris(2‐pyridylmethyl)amine‐based stereodynamic probe

et al. 2019

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“…Variable‐temperature ECD spectra were run with a home‐made Peltier apparatus designed cylindrical cells, equipped with an Ascon MS 30 controller (±1°C accuracy). ECD solid‐state spectrum was recorded as a KCl pellet using the protocol developed previously . VCD and IR spectra were recorded using a Jasco FVS–6000 VCD spectrometer with the following conditions: resolution 4 cm −1 ; range 2000–900 cm −1 ; 4000 accumulations.…”

Section: Methodsmentioning

confidence: 99%

Synthesis and structure analysis of ferrocene‐containing pseudopeptides

et al. 2018

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Ferrocene with its aromaticity and facile redox properties is an attractive moiety to be incorporated into functional moieties. Medicinal applications of ferrocene are well known and ferrocene itself shows cytotoxic and antianemic properties. In this article, we will describe the synthesis and the structure analysis of two pseudopeptides containing a ferrocene moiety as N-terminal group. After purification, Fc-l-Phe-d-Oxd-OBn [l-Phel-phenylalanine; d-Oxd(4R,5S)-4-Methyl-5-carboxy-oxazolidin-2-one] appears as bright brown solid that spontaneously forms brown needles. The X-ray diffraction of the crystals shows the presence of strong π interactions between the ferrocenyl moiety and the phenyl rings, while no NH•••OC hydrogen bonds are formed. This result is confirmed by FT-IR and H NMR analysis. In contrast, both FT-IR and H NMR analysis suggest that Fc-(l-Phe-d-Oxd) -OBn forms a turn conformation stabilized by intramolecular NH•••OC hydrogen bonds in solution. Chiroptical spectroscopies (ECD and VCD) substantially confirmed the absence of a well-defined folded structure. The presence of the Fc moiety is responsible for specific ECD signals, one of which displayed pronounced temperature dependence and is directly related with the helicity assumed by the Fc core. Solid-state ECD spectra were recorded and rationalized on the basis of the X-ray geometry and quantum-mechanical calculations.

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“…Unusually large VCD is also often observed for transition metal complexes, containing Co 2+ , Co 3+ , Ni 2+ , and other coordinating ions . Clearly, this effect must be different than for the condensation‐induced enhancement observed for the nucleic acids, fibrils and crystals.…”

Section: Vibrational Circular Dichroismmentioning

confidence: 99%

Recent Trends in Chiroptical Spectroscopy: Theory and Applications of Vibrational Circular Dichroism and Raman Optical Activity

2020

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Chiroptical spectroscopy exploring the interaction of matter with polarized light provides many tools for molecular structure and interaction studies. Here, some recent discoveries are reviewed, primarily in the field of vibrational optical activity. Technological advances results in the development of more sensitive vibrational circular dichroism (VCD), Raman optical activity (ROA) or circular polarized luminescence (CPL) spectrometers. Significant contributions to the field also come from the light scattering and electronic structure theories, and their implementation in computer systems. Finally, new chiroptical phenomena have been observed, such as enhanced circular dichroism of biopolymers (protein fibrils, nucleic acids), plasmonic and resonance chirality‐transfer ROA experiments. Some of them are not yet understood or attributed to instrumental artifacts so far. Nevertheless, these unknown territories also indicate the vast potential of the chiroptical spectroscopy, and their investigation is even more challenging.

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Co(ii)-induced giant vibrational CD provides a new design of methods for rapid and sensitive chirality recognition

Cited by 41 publications

References 20 publications

Extending substrate sensing capabilities of zinc tris(2‐pyridylmethyl)amine‐based stereodynamic probe

Extending substrate sensing capabilities of zinc tris(2‐pyridylmethyl)amine‐based stereodynamic probe

Synthesis and structure analysis of ferrocene‐containing pseudopeptides

Recent Trends in Chiroptical Spectroscopy: Theory and Applications of Vibrational Circular Dichroism and Raman Optical Activity

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