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

Abstract

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.

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

“…[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.…”

“…[48][49][50][51] In the recent years, we have reported several examples on the catalytic and recognition capabilities of tripodal ligands, especially focusing on the TPMA molecular sensing toward α-amino acids ( Figure 1). 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.…”

Supramolecular cages as differential sensors for dicarboxylate anions: guest length sensing using principal component analysis of ESI-MS and 1H-NMR raw data

“…[26][27][28] In particular, it is possible to employ complex systems characterized by multiple equilibria which can be perturbed by the presence of an analyte toward a particular product distribution. In this context, we have recently developed a new class of supramolecular structures, [29][30][31][32][33] in particular molecular cages, which have been synthesized using imine dynamic covalent chemistry (DCC). These cages are obtained by self-assembly of modied tris(-pyridylmethyl)amine (TPMA) complexes and different diamine linkers.…”

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

“…Recently, we have started to combine the TPMA scaffold with dynamic covalent chemistry (DCC) of imines formation . DCC has already shown its fundamental role in the formation of new complex nano‐architectures.…”

“…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.…”