From substituent effects to applications: enhancing the optical response of a four-component assembly for reporting ee values

Lin, Chung-Yon; Giuliano, Michael W.; Ellis, Bryan D.; Miller, Scott J.; Anslyn, Eric V.

doi:10.1039/c5sc04629g

Cited by 23 publications

(29 citation statements)

References 22 publications

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“…7,11,12 The analyte sterics were parametrized with LFERs such as those of Taft and Charton. In this Communication, we describe an alternate application for LFERs: training sets for model building in an analytical application.…”

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confidence: 99%

“…7,11,12 The analyte sterics were parametrized with LFERs such as those of Taft and Charton. 7,11,12 The analyte sterics were parametrized with LFERs such as those of Taft and Charton.…”

mentioning

confidence: 99%

“…Taft parameters were developed by measuring rates of acid-catalyzed hydrolysis of substituted methyl esters (RCOOMe), where the changes in rate were a result of steric interactions between the R group and the nucleophile. 12 In the present study, we used the 3-methyl variant of the CDactive assembly with a training set of nine alcohols ( Figure 1). 35,36 To explore whether predictive correlations could be created for CD ellipticities, we examined the multicomponent assembly shown in Scheme 1.…”

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confidence: 99%

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Model Building Using Linear Free Energy Relationship Parameters–Eliminating Calibration Curves for Optical Analysis of Enantiomeric Excess

2016

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Linear free energy relationship (LFER) parameters are routinely used to parametrize physicochemical effects while investigating reaction mechanisms. In this Communication, we describe an alternate application for LFERs: training sets for model building in an analytical application. In this study, the sterics, quantified by Charton parameters (Δv), of nine secondary chiral alcohol analytes were correlated to the circular dichroism output from a chiral alcohol optical sensor. To test the validity of the model, the correlative linear model was applied to determine the enantiomeric excess of samples of two alcohols without a priori knowledge of a calibration curve. The error in this method was comparable to those of previous experimental methods (<5%).

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confidence: 99%

“…7,11,12 The analyte sterics were parametrized with LFERs such as those of Taft and Charton. 7,11,12 The analyte sterics were parametrized with LFERs such as those of Taft and Charton.…”

mentioning

confidence: 99%

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confidence: 99%

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Model Building Using Linear Free Energy Relationship Parameters–Eliminating Calibration Curves for Optical Analysis of Enantiomeric Excess

2016

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“…Anslyn [30][31][32][33][34][35][36] and their co-workers with tris(2-pyridylmethyl)amine (TPMA) metal complexes.…”

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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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“…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 . 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).…”

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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From substituent effects to applications: enhancing the optical response of a four-component assembly for reporting ee values

Cited by 23 publications

References 22 publications

Model Building Using Linear Free Energy Relationship Parameters–Eliminating Calibration Curves for Optical Analysis of Enantiomeric Excess

Model Building Using Linear Free Energy Relationship Parameters–Eliminating Calibration Curves for Optical Analysis of Enantiomeric Excess

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

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