Fluorescent probes for biothiols have aroused increasing interest owing to their potential to enable better understanding of the diverse physiological and pathological processes related to the biothiol species. BODIPY fluorophores exhibit excellent optical properties, which can be readily tailored by introducing diverse functional units at various positions of the BODIPY core. In the present review, the development of fluorescent probes based on BODIPYs for the detection of biothiols are systematically summarized, with emphasis on the preferable detection of individual biothiols, as well as simultaneous discrimination among cysteine (Cys), homocysteine (Hcy), reduced glutathione (GSH). In addition, organelle-targeting probes for biothiols are also highlighted. The general design principles, various recognition mechanisms, and biological applications are elaboratively discussed, which could provide a useful reference to researchers worldwide interested in this area.

BODIPY-Based Fluorescent Probes for Biothiols

Dipyrrins serve as monovalent bidentate ligand molecules that coordinate to various cations. Their BF2 complexes, 4,4-difluoro-4-bora-3a,4a-diaza-s-indacene and its derivatives (BODIPYs), exhibit excellent photostability, strong light absorption, and high fluorescence quantum yield, thereby encouraging their application in various fields, e.g., as biological and biomedical fluorescent markers. Dipyrrin may also accept a wide variety of metal ions spontaneously. However, dipyrrin metal complexes have been disregarded from materials science research. This review article summarizes recent progress in bis(dipyrrinato)metal(II) and tris(dipyrrinato)metal(III) complexes from the viewpoint of materials chemistry. Section 2 describes a series of efforts aimed to realize intense luminescence superior to or comparable with that of BODIPYs. The spontaneous coordination of these complexes enables them to construct self-assembled nanoarchitectures, such as supramolecules and coordination polymers that form one-dimensional nanowires, two-dimensional nanosheets, and metal–organic frameworks. Section 3 describes such alluring molecular superstructures. Section 4 discusses potential applications based on these nanoarchitectures, such as thermoelectric and photoelectric conversion.

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New aspects in bis and tris(dipyrrinato)metal complexes: bright luminescence, self-assembled nanoarchitectures, and materials applications

A near-infrared BODIPY-based fluorescent probe for ratiometric and discriminative detection of Hg2+ and Cu2+ ions in living cells

Fluorescent indicators of metal ions based on dipyrrоmethene platform

Highly sensitive and selective chemosensor for Cu2+ and H2PO4− based on coumarin fluorophore

New luminophors based on the binuclear helicates of d-METALS with BIS(DIPYRRIN)S

• Photostability and 1 O 2 generation of halogenated [ML 2 ] and [BF 2 L] has been studied. • The photodestruction processes of dyes include the initial stages of dehalogenation. • Halogenated dipyrromethenates exhibit high efficiency of singlet oxygen generation. • The complexes photostability increases upon going from iodo- to bromosubstituted dyes. A comparative analysis of the influence of the molecular structure and medium properties on the photostability and efficiency of singlet oxygen generation by luminophores based on iodo- and bromosubstituted zinc(II), cadmium(II) and boron(III) dipyrromethenates is presented. It has been established that photodestruction of halogen-substituted complexes [ZnL 2 ], [CdL 2 ], and [BF 2 L] includes the initial stages of dehalogenation of luminophores and is a process of photosensitization, the efficiency of which depends both on the molecular structure of the chelates and on the medium properties. Based on experimental and literature data, the mechanism of 1 O 2 generation with the participation of iodo- and bromosubstituted dipyrromethenates [ZnL 2 ], [CdL 2 ] and [BF 2 L] was proposed and substantiated. It was shown that the indices of photostability and generation of singlet oxygen by heteroligand boron chelates [BF 2 L] are approximately 33 and 8 times higher, respectively, than the corresponding characteristics of homoligand complexes [ZnL 2 ] and [CdL 2 ]. The influence of the halogenation features is manifested in an increase of the photodegradation efficiency upon the transition from 2-monoiodo- to 3,5-dibromo- and 2,6-dibromosubstituted dipyrromethenates of zinc(II), cadmium(II) and boron(III) due to a decrease in the probability the transition to a triplet excited state and a decrease in the efficiency of singlet oxygen generation. The combination of the high photostability rates and singlet oxygen generation provides a good practical potential for the use of iodo- and bromosubstituted zinc(II), cadmium(II), and boron(III) dipyrromethenates as PDT agents. 

Influence of structural and solvation factors on the photodestruction and efficiency of singlet oxygen generation by luminophores based on iodo- and bromosubstituted zinc(II), cadmium(II) and boron(III) dipyrromethenates

Chemistry and Practical Application of Dipyrromethene Ligands, Salts, and Coordination Compounds as Optical Sensors for Analytes of Various Nature (A Review)

Anatolij I. V'yugin

Papers

Fluorescent indicators of metal ions based on dipyrrоmethene platform

New luminophors based on the binuclear helicates of d-METALS with BIS(DIPYRRIN)S

Influence of structural and solvation factors on the photodestruction and efficiency of singlet oxygen generation by luminophores based on iodo- and bromosubstituted zinc(II), cadmium(II) and boron(III) dipyrromethenates

Chemistry and Practical Application of Dipyrromethene Ligands, Salts, and Coordination Compounds as Optical Sensors for Analytes of Various Nature (A Review)