OFF‐ON‐OFF Red‐Emitting Fluorescent Indicators for a Narrow pH Window

Cidlina, Antonin; Miletín, Miroslav; Fathi-Rasekh, Mahtab; Nemykin, Victor N.; Zimčík, Petr; Novakova, Veronika

doi:10.1002/chem.201604978

Cited by 18 publications

(12 citation statements)

References 45 publications

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“…TFA treatment led to the recovery of the emission spectrum. The observed reversible optical switching could pave the way to the development of molecular switches and pH sensors. , …”

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confidence: 92%

“…The observed reversible optical switching could pave the way to the development of molecular switches and pH sensors. 42,43 To interpret the results of NMR experiments, the nucleusindependent chemical shift, NICS(1), 22,44 and theoretical 1 H and 13 C NMR spectra were calculated for 1 + and [1+OH] using the gauge independent atomic orbital (GIAO) method 45 (Figure 4a,b and Figure S30). For 1 + substantially negative NICS(1) values are evenly distributed among subrings, which points to strong aromaticity of both the inner annulene and peripheral benzene rings.…”

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confidence: 99%

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Switchable Aromaticity of Phthalocyanine via Reversible Nucleophilic Aromatic Addition to an Electron-Deficient Phosphorus(V) Complex

et al. 2021

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Reversible nucleophilic addition to a phthalocyanine core was observed for the first time for the electron-deficient cationic phosphorus(V) complex [PcP(OMe) 2 ] + , whose reaction with KOH afforded a highly distorted nonaromatic adduct bearing an OH group at one of the α-pyrrolic carbon atoms. This adduct was characterized by single-crystal X-ray diffraction, ESI HRMS, and NMR, and UV−vis spectroscopy, together with quantum-chemical modeling. The acidic treatment of this adduct restored aromaticity and recovered the starting cationic complex. The reversible aromaticity breakage resulted in dramatic changes in the photophysical properties of the studied complex, which could pave the way to novel switchable Pc-based compounds and materials.

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“…TFA treatment led to the recovery of the emission spectrum. The observed reversible optical switching could pave the way to the development of molecular switches and pH sensors. , …”

mentioning

confidence: 92%

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confidence: 99%

Switchable Aromaticity of Phthalocyanine via Reversible Nucleophilic Aromatic Addition to an Electron-Deficient Phosphorus(V) Complex

et al. 2021

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“…Facile formation of stable, long-lived, and charge-separated states is an important initial step in the preparation of efficient organic solar cells. − There are many examples of covalently bound donor–acceptor (D–A) systems, where strong binding provides stability and some degree of design control over the electronic coupling. − When substituted with electron-donating groups capable of intramolecular electron transfer, porphyrins, − phthalocyanines, − subphthalocyanines, − boron-dipyrromethenes (BODIPYs), − and boron-azadipyrromethenes (aza-BODIPYs) − have been demonstrated to be effective and stable assemblies for initial light absorption and charge separation. Organic amines − and ferrocene, − as examples, have been show...…”

Section: Introductionmentioning

confidence: 99%

1,7-Dipyrene-Containing Aza-BODIPYs: Are Pyrene Groups Effective as Ligands To Promote and Direct Complex Formation with Common Nanocarbon Materials?

et al. 2018

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A series of 1,7-dipyrene-aza-BODIPY and 1,7-dipyrene-3,5-diferrocene-aza-BODIPY derivatives 5a–e with pyrene ligands covalently attached to the β-pyrrolic positions of the boron-azadipyrromethene (aza-BODIPY) core have been prepared and characterized by NMR, UV–vis, and steady-state fluorescence spectroscopy; high-resolution mass spectrometry; and X-ray crystallography. The redox processes of these donor–acceptor aza-BODIPY systems were investigated by electrochemistry (cyclic voltammetry and differential pulse voltammetry methods) and spectroelectrochemistry. The potential of the closely spaced 1,7-dipyrene fragments to promote formation of noncovalent π-complexes with nanocarbon materials (C60, C70, (6,5)-single-walled carbon nanotube, and graphene) was explored. UV–vis, steady-state fluorescent, and time-resolved transient absorption spectroscopy data indicated that the interaction between the new pyrene-aza-BODIPYs and C60 or C70 fullerenes in solution is weak, and time-resolved transient absorption spectroscopy provided no evidence of photoinduced electron transfer. X-ray crystallography on a binary solid of aza-BODIPYs 5b and C60 was indicative of a pyrene–pyrene rather than pyrene–C60 interaction motif, whereas fullerenes were found to form close contacts with the electron-rich B,O-chelated part of aza-BODIPY 5b. In contrast, pyrene–pyrene and pyrene–C60 but not aza-BODIPY–C60 interactions were observed in the crystal structure of aza-BODIPY 5d and C60. Density functional theory (DFT) and time-dependent DFT calculations were used to support conclusions based on experimental data and are suggestive of rather weak interaction energies between 1,7-dipyrene-aza-BODIPYs and nanocarbon materials. Direct comparison with an analogous control compound lacking the pyrene ligands demonstrated that the pyrene substituents were ineffective at promoting and directing complex formation with nanocarbon materials. A common measurement of complex formation, emission loss in the presence of a nanocarbon acceptor, was demonstrated to have an alternative explanation in these systems, and the general effectiveness of using pyrene ligands to build noncovalent complexes was drawn into question.

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“…A previous report of the emission properties of protonated 2 generated in solution recorded a decrease in the quantum yield to 0.01, lower than that observed for the isolated 2HCl [52] . In addition, a zinc complex of a phthalocyanine analogue was shown to have a “Turn‐Off” effect from protonation of the meso ‐N when acidified in solution [56] . The studies reported herein suggest that the isolation of the pure species for the side‐pocket protonated PcM produces stronger emission in this case.…”

Section: Resultsmentioning

confidence: 77%

Preferential Formation of Side‐Pocket‐Substituted Zinc Phthalocyanines Emitting Beyond 800 nm

et al. 2021

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A series of zinc (1,4,8,11,15,18,22,25‐octabutoxy)phthalocyanine (2) complexes that spontaneously form 5‐coordinate complexes with anionic axial ligands neutralized with side‐pocket cations, of the form Cation‐PcZnX (X=Cl, OAc; Cation=H+ or Li+), was synthesized and structurally characterized. The side‐pocket protonation of the axial‐chloride species pushed the emission maximum from 760 nm (for axial ligand‐free 2) to 826 nm, well into the NIR region. A 1D‐coordinated chain bridged by lithium and chloride atoms was isolated and structurally characterized, representing the first side‐pocket metalated PcM species. This preferential formation of axially substituted [PcZnX]− “ate” complexes and their sequestration of both protons and lithium cations, opens a new series of materials with unique structural and electronic properties. Furthermore, their ability to both absorb and emit in the NIR region makes them desirable for numerous applications.

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OFF‐ON‐OFF Red‐Emitting Fluorescent Indicators for a Narrow pH Window

Cited by 18 publications

References 45 publications

Switchable Aromaticity of Phthalocyanine via Reversible Nucleophilic Aromatic Addition to an Electron-Deficient Phosphorus(V) Complex

Switchable Aromaticity of Phthalocyanine via Reversible Nucleophilic Aromatic Addition to an Electron-Deficient Phosphorus(V) Complex

1,7-Dipyrene-Containing Aza-BODIPYs: Are Pyrene Groups Effective as Ligands To Promote and Direct Complex Formation with Common Nanocarbon Materials?

Preferential Formation of Side‐Pocket‐Substituted Zinc Phthalocyanines Emitting Beyond 800 nm

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