Extended dipyrrin ligands: candidates for optical metal ion detection under competitive conditions

Guski, S.; Albrecht, Markus; Willms, Thomas; Nabeshima, Tatsuya; Pan, Fuchao; Puttreddy, Rakesh

doi:10.1039/c7cc00672a

Cited by 10 publications

(6 citation statements)

References 31 publications

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“…Dipyrrin ligands accept not only the BF 2 moiety, but also various transition-metal ions to give the corresponding complexes. [73][74][75] As is the case with the BODIPY oligomers, transition-metal complexes of the oligodipyrrins often show unique structures and properties that are difficult to be achieved by the corresponding monomeric complexes. 76,77 In particular, conformationally flexible macrocyclic oligodipyrrin ligands produced uniquely shaped multinuclear complexes having characteristic properties such as helical-chirality induction by a chiral guest molecule 78 and a temperature-dependent springlike conformational change.…”

Section: A Cyclic Oligomer Of Zinc-dipyrrin Complexesmentioning

confidence: 99%

Synthesis and Functions of Oligomeric and Multidentate Dipyrrin Derivatives and their Complexes

Chiba¹,

Nakamura²,

Matsuoka³

et al. 2020

Synlett

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The dipyrrin–metal complexes and especially the boron complex 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene (BODIPY) have recently attracted considerable attention because of their interesting properties and possible applications. We have developed two unique and useful ways to extend versatility and usefulness of the dipyrrin complexes. The first one is the linear and macrocyclic oligomerization of the BODIPY units. These arrangements of the B–F moieties of the oligomerized BODIPY units provide sophisticated functions, such as unique recognition ability toward cationic guest, associated with changes in the photophysical properties by utilizing unprecedented interactions between the B–F and a cationic species. The second one is introduction of additional ligating moieties into the dipyrrin skeleton. The multidentate N2Ox dipyrrin ligands thus obtained form a variety of complexes with 13 and 14 group elements, which are difficult to synthesize using the original N2 dipyrrin derivatives. Interestingly, these unique complexes exhibit novel structures, properties, and functions such as guest recognition, stimuli-responsive structural conversion, switching of the optical properties, excellent stability of the neutral radicals, etc. We believe that these multifunctional dipyrrin complexes will advance the basic chemistry of the dipyrrin complexes and develop their applications in the materials and medicinal chemistry fields.1 Introduction2 Linear Oligomers of Boron–Dipyrrin Complexes3 Cyclic Oligomers of Boron–Dipyrrin Complexes4 A Cyclic Oligomer of Zinc–Dipyrrin Complexes5 Group 13 Element Complexes of N2Ox Dipyrrins6 Chiral N2 and N2Ox Dipyrrin Complexes7 Group 14 Element Complexes of N2O2 Dipyrrins8 Other N2O2 Dipyrrin Complexes with Unique Properties and Functions9 Conclusion

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Section: A Cyclic Oligomer Of Zinc-dipyrrin Complexesmentioning

confidence: 99%

Synthesis and Functions of Oligomeric and Multidentate Dipyrrin Derivatives and their Complexes

Chiba¹,

Nakamura²,

Matsuoka³

et al. 2020

Synlett

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“…Dipyrromethenes, commonly referred to as dipyrrins, are a versatile class of organic dyes capable of complexation of metal ions. − Boron complexes of dipyrrins, known as BODIPY, − are one of the most investigated classes of chromophores with applications ranging from laser dyes , to chemosensors , and fluorescent switches . In contrast, metal complexes of dipyrrins, originally described nearly a century ago, have been explored much less, although recent developments in the synthetic chemistry of dipyrrins, combined with the unusual photophysical behavior of their complexes reinvigorated interest in these potent chromophores. ,− For practical purposes, metallodipyrrins are being explored as dyes for light-harvesting applications, − building blocks for metal–organic frameworks, and other supramolecular assemblies. ,− In addition, the ability of some dipyrrins to undergo chromo/fluorogenic complexation with metal ions ,,− prompts exploration of their potential in biological sensing of Zn 2+ and other divalent cations.…”

Section: Introductionmentioning

confidence: 99%

“…On the other hand, the ability to sense extracellular Zn 2+ presents interest for studies of several biological processes, including the release of insulin by pancreatic β-cells ,, and fertilization of the mammalian egg, , and water-soluble membrane-impermeable dipyrrins can potentially fill that niche. To the best of our knowledge, presently, there exist only a few dipyrrins capable of formation of complexes with Zn 2+ in aqueous media. ,, …”

Section: Introductionmentioning

confidence: 99%

Unusual Reactivity and Metal Affinity of Water-Soluble Dipyrrins

2022

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Dipyrrins are a versatile class of organic ligands capable of fluorogenic complexation of metal ions. The primary goal of our study was to evaluate dipyrrins functionalized with ester and amide groups in 2,2′-positions in sensing applications. While developing the synthesis, we found that 3,3′,4,4′-tetraalkyldipyrrins 2,2′-diesters as well as 2,2′-diamides can undergo facile addition of water at the meso-bridge, transforming into colorless mesohydroxydipyrromethanes. Spectroscopic and computational investigation revealed that this transformation proceeds via dipyrrin cations, which exist in equilibrium with the hydroxydipyrromethanes. While trace amounts of acid favor conversion of dipyrrins to hydroxydipyrromethanes, excess acid shifts the equilibrium toward the cations. Similarly, the presence of Zn 2+ facilitates elimination of water from hydroxydipyrromethanes with chromogenic regeneration of the dipyrrin system. In organic solutions in the presence of Zn 2+ , dipyrrin-2,2′-diesters exist as mixtures of mono-(LZnX) and bis-(L 2 Zn) complexes. In L 2 Zn, the dipyrrin ligands are oriented in a nonorthogonal fashion, causing strong exciton coupling. In aqueous solutions, dipyrrins bind Zn 2+ in a 1:1 stoichiometry, forming mono-dipyrrinates (LZnX). Unexpectedly, dipyrrins with more electron-rich 2,2′-carboxamide groups revealed ∼20-fold lower affinity for Zn 2+ than the corresponding 2,2′-diesters. Density Functional Theory (DFT) calculations with explicit inclusion of water reproduced the observed trends and allowed us to trace the low affinity of the dipyrrin-diamides to the stabilization of the corresponding free bases via hydrogen bonding with water molecules. Overall, our results reveal unusual trends in the reactivity of dipyrrins and provide clues for the design of dipyrrin-based sensors for biological applications.

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“…While several paramagnetic dipyrrinato complexes have been reported, [41][42][43][44][45][46][47][48][49][50][51][52] their emission spectra have rarely been described, with the exception of a report of weak fluorescence from homoleptic Cu(II) dipyrrins, 53 though quantum efficiencies of luminescence were not reported. Both dia-and paramagnetic luminophores have potential utility as metal sensors, 6,54 in imaging applications, 7 and for paramagnetic luminophores especially, as hybrid optical/MRI imaging agents. 8 Following protocols for dipyrrin halogenation previously reported, 49 the parent dipyrrin ( Ar L)H (( Ar L)H: 1,9-bis(2′,4′,6′triphenylphenyl)-5-mesityl-dipyrrin) could be brominated with N-bromosuccinimide in tetrahydrofuran (THF) in good yield (72%, Scheme 1); whereas iodination with NIS required camphor sulfonic acid (CSA) catalysis and longer reaction times (65%).…”

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confidence: 99%