Bis(zinc porphyrin) as a CD-sensitive bidentate host molecule: direct determination of absolute configuration of mono-alcohols

Hayashi, Satoshi; Yotsukura, Miku; Noji, Masahiro; Takanami, Toshikatsu

doi:10.1039/c5cc03303a

Cited by 50 publications

(37 citation statements)

References 52 publications

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“…[5][6][7][8] Among the different techniques, electronic circular dichroism is dominant, even though alternative techniques have been extensively studied as well. [15][16][17][18][19][20] Among this class of systems, which are usually defined as stereodynamic optical probes, metal complexes have assumed a key role. [15][16][17][18][19][20] Among this class of systems, which are usually defined as stereodynamic optical probes, metal complexes have assumed a key role.…”

Section: Introductionmentioning

confidence: 99%

Second‐Generation Tris(2‐pyridylmethyl)amine–Zinc Complexes as Probes for Enantiomeric Excess Determination of Amino Acids

et al. 2017

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Self‐assembly through imine condensation chemistry in combination with metal coordination is becoming one of the leading strategies for the preparation of stereodynamic probes for the determination of enantiomeric excess. Recently, we reported a novel molecular architecture based on a modified tris(2‐pyridylmethyl)amine–zinc(II) complex [TPMA = tris(2‐pyridylmethyl)amine] that is able to function as an optical probe for the determination of the enantiomeric excess of amino acids. Herein, we report on how a slight modification of the TPMA ligand enhances both the dichroic response and the stability of the system. The novel probe provides a much higher dichroic signal compared with the previously reported system.

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Section: Introductionmentioning

confidence: 99%

Second‐Generation Tris(2‐pyridylmethyl)amine–Zinc Complexes as Probes for Enantiomeric Excess Determination of Amino Acids

et al. 2017

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“…[1][2][3][4] In this context, several supramolecular architectures have been developed to gather an optical signal that can be easily measured through the most common spectroscopic techniques, ie, circular dichroism (CD). [5][6][7][8][9][10][11][12][13][14][15] Usually, these supramolecular sensors possess at least one labile stereogenic element that interconverts between 2 enantiomeric forms. The addition of a chiral analyte leads preferentially to the formation of one diasteroisomer that furnishes back the optical chiral information.…”

Section: Introductionmentioning

confidence: 99%

A stereodynamic fluorescent probe for amino acids. Circular dichroism and circularly polarized luminescence analysis

et al. 2017

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The use of stereodynamic probes is becoming one of the leading strategies for the fast and effective determination of enantiomeric excess. Recently, we reported a series of novel molecular architectures based on a modified tris(2-pyridylmethyl)amine complex (TPMA), which are able to amplify the electronic CD, in the case of Zn(II) assemblies and vibrational CD, in the case of Co(II) assemblies. Herein, we report a structural modification of the ligand with the purpose to obtain a fluorescent chiral probe. The study deals with the synthesis of the novel ligand, the formation of the self-assembly system with amino acids, and the study of the electronic CD and circularly polarized luminescence. KEYWORDS CD, CPL, enantiomeric excess, self-assembly, supramolecular chemistry | INTRODUCTIONIn the last few decades, several research groups have been studying chiral sensors because of the important applications that chiral molecules have in several fields of science, ranging from catalysis to materials. Under this respect, special attention has been paid to searching new methods and techniques for the determination of enantiomeric excess (ee) that are faster and cheaper than traditional chromatographic methods. [1][2][3][4] In this context, several supramolecular architectures have been developed to gather an optical signal that can be easily measured through the most common spectroscopic techniques, ie, circular dichroism (CD). [5][6][7][8][9][10][11][12][13][14][15] Usually, these supramolecular sensors possess at least one labile stereogenic element that interconverts between 2 enantiomeric forms. The addition of a chiral analyte leads preferentially to the formation of one diasteroisomer that furnishes back the optical chiral information. Within these stereodynamic probes, tris(2-pyridylmethyl)amine (TPMA)-based metal complexes have shown to be versatile chemical systems for the determination of ee. [16][17][18][19][20][21][22] This ligand assumes a propeller-like arrangement around the metal center that in solution is in equilibrium between the two helical configurations (clockwise and counterclockwise configuration is preferred, and the resulting diasteroisomer is able to provide a chiroptical signal. 23,24 Recently, we have started to combine the TPMA scaffold with dynamic covalent chemistry (DCC) of imines formation. [25][26][27][28][29]31 has already shown its fundamental role in the formation of new complex nano-architectures. In particular, we described two novel supramolecular architectures based on modified TPMA metal complexes (Scheme 1): the dinuclear 1-Zn-aa and 3-Zn-aa, and the trinuclears 2-Zn-aa and 2-Co-aa. These systems have shown to perform as probes for amino acids, 32-35 furnishing dichroic signals characteristic of the amino acidic side chain and proportional to the enantiomeric excess. While all systems are effective using electronic CD, the presence of cobalt(II) in 2-Co-aa induces additionally gigantic (or: huge) vibrational CD bands, allowing the measurement of a VCD spectrum in onl...

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“…However, because of the weak binding affinity of alcohols to metal centres, very few studies were reported 12–14 . For example, Borovkov and co-workers reported the ethane-bridged bisporphyrin system.…”

Section: Introductionmentioning

confidence: 99%

Host-guest assembly for highly sensitive probing of a chiral mono-alcohol with a zinc trisporphyrinate

Zhuo

et al. 2017

Sci Rep

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A zinc trisporphyrinate has been developed as a chirality sensor for chiral mono-alcohols. In its structure, there are two “spaces” surrounded by three porphyrin moieties, which allow guests to fill in. It has shown extremely high CD sensitivity for a chiral mono-alcohol with a naphthyl substituent, 1-(1-naphthyl)ethanol, at μM level, which is at least three orders of magnitude lower concentration than previous reports. A crystallographic study of the host-guest complex reveals the binding of 1-(1-naphthyl)ethanol to the zinc trisporphyrinate is greatly enhanced by multipoint interactions, such as coordination interactions, hydrogen bonding, π-π and CH···π interactions etc. Spectroscopic studies suggest the corresponding binding constant K1 is over 105 M−1, which is two or three orders of magnitude larger than other mono-alcohols. Among porphyrin systems, this trisporphyrin have the strongest binding affinity for 1-(1-naphthyl)ethanol, which leads to the highest CD sensitivity.

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Bis(zinc porphyrin) as a CD-sensitive bidentate host molecule: direct determination of absolute configuration of mono-alcohols

Cited by 50 publications

References 52 publications

Second‐Generation Tris(2‐pyridylmethyl)amine–Zinc Complexes as Probes for Enantiomeric Excess Determination of Amino Acids

Second‐Generation Tris(2‐pyridylmethyl)amine–Zinc Complexes as Probes for Enantiomeric Excess Determination of Amino Acids

A stereodynamic fluorescent probe for amino acids. Circular dichroism and circularly polarized luminescence analysis

Host-guest assembly for highly sensitive probing of a chiral mono-alcohol with a zinc trisporphyrinate

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