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Tripyrrin-armed isosmaragdyrins: synthesis, heterodinuclear coordination, and protonation-triggered helical inversion.

ABSTRACT: Oxidative ring closure of linear oligopyrroles is one of the synthetic approaches to novel porphyrinoids with dinuclear coordination sites and helical chirality. The spatial arrangement of the pyrrolic groups of octapyrrole (P8) affected the position of the intramolecular oxidative coupling of the pyrrolic units; tripyrrin-armed isosmaragdyrin analogue (1) containing a β,β-linked bipyrrole moiety was synthesized regioselectively in a high yield by using FeCl₃. Ni^II-coordination at the armed tripyrrin site of 1 allowed the formation of diastereomeric helical twisted complexes (2A and 2B) and succeeding Cu^II-coordination at the macrocyclic core afforded heterodinuclear Ni^II/Cu^II-complexes (3A and 3B). Each of them comprised a pair of separable enantiomers, exhibiting P- and M-helices, respectively. Notably, diastereomeric interconversion from 2A to 2B was quantitatively achieved as a consequence of helical transformation under acidic conditions.

SUBMITTER: Li C

PROVIDER: S-EPMC8157612 | biostudies-literature | 2020 Feb

REPOSITORIES: biostudies-literature

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Tripyrrin-armed isosmaragdyrins: synthesis, heterodinuclear coordination, and protonation-triggered helical inversion.

Li Chengjie C Zhang Kai K Ishida Masatoshi M Li Qizhao Q Shimomura Keito K Baryshnikov Glib G Li Xin X Savage Mathew M Wu Xin-Yan XY Yang Sihai S Furuta Hiroyuki H Xie Yongshu Y

Chemical science 20200204 10

Oxidative ring closure of linear oligopyrroles is one of the synthetic approaches to novel porphyrinoids with dinuclear coordination sites and helical chirality. The spatial arrangement of the pyrrolic groups of octapyrrole (P8) affected the position of the intramolecular oxidative coupling of the pyrrolic units; tripyrrin-armed isosmaragdyrin analogue (1) containing a β,β-linked bipyrrole moiety was synthesized regioselectively in a high yield by using FeCl3. NiII< ...[more]

PMID: 34084339

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Project description:We report kinetically controlled chiral supramolecular polymerization based on ligand-metal complex with a 3 : 2 (L : Ag+) stoichiometry accompanying a helical inversion in water. A new family of bipyridine-based ligands (d-L1, l-L1, d-L2, and d-L3) possessing hydrazine and d- or l-alanine moieties at the alkyl chain groups has been designed and synthesized. Interestingly, upon addition of AgNO3 (0.5-1.3 equiv.) to the d-L1 solution, it generated the aggregate I composed of the d-L1AgNO3 complex (d-L1 : Ag+ = 1 : 1) as the kinetic product with a spherical structure. Then, aggregate I (nanoparticle) was transformed into the aggregate II (supramolecular polymer) based on the (d-L1)3Ag2(NO3)2 complex as the thermodynamic product with a fiber structure, which led to the helical inversion from the left-handed (M-type) to the right-handed (P-type) helicity accompanying CD amplification. In contrast, the spherical aggregate I (nanoparticle) composed of the d-L1AgNO3 complex with the left-handed (M-type) helicity formed in the presence of 2.0 equiv. of AgNO3 and was not additionally changed, which indicated that it was the thermodynamic product. The chiral supramolecular polymer based on (d-L1)3Ag2(NO3)2 was produced via a nucleation-elongation mechanism with a cooperative pathway. In thermodynamic study, the standard ΔG° and ΔH e values for the aggregates I and II were calculated using the van't Hoff plot. The enhanced ΔG° value of the aggregate II compared to that of the formation of aggregate I confirms that aggregate II was thermodynamically more stable. In the kinetic study, the influence of concentration of AgNO3 confirmed the initial formation of the aggregate I (nanoparticle), which then evolved to the aggregate II (supramolecular polymer). Thus, the concentration of the (d-L1)3Ag2(NO3)2 complex in the initial state plays a critical role in generating aggregate II (supramolecular polymer). In particular, NO3 - acts as a critical linker and accelerator in the transformation from the aggregate I to the aggregate II. This is the first example of a system for a kinetically controlled chiral supramolecular polymer that is formed via multiple steps with coordination structural change.

Dataset Information

Tripyrrin-armed isosmaragdyrins: synthesis, heterodinuclear coordination, and protonation-triggered helical inversion.

Publications

Tripyrrin-armed isosmaragdyrins: synthesis, heterodinuclear coordination, and protonation-triggered helical inversion.

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