BODIPY dyes and their derivatives: syntheses and spectroscopic properties.

The total synthesis of chlorophyll a

The use of α,β-unsubstituted dipyrrins, dpm, for the elaboration of infinite architectures in crystalline form based on coordination as well as hydrogen bonding interactions is reviewed. These ligands can be readily functionalized and derivatives bearing either a peripheral hydrogen bond donor/acceptor group or a secondary coordinating group have been developed. In the first case, the complexes incorporating these dpms self-assemble via hydrogen bonding leading to extended architectures. In the second case, the coordinating complexes, or metallatectons, can self-assemble to form homonuclear networks such as in a series of (acac)Cu(dpm) complexes. Upon association of the metallatectons with a second metal centre, heterometallic architectures are formed. These MOFs are constructed by coordination as well as Ag-π interactions depending on the nature of the peripheral coordinating group and the coordination geometry of the metallatecton.

Dipyrrin based homo- and hetero-metallic infinite architectures

The synthesis and properties of a new family of π-extended dipyrrins capable of forming brightly fluorescent complexes with metal ions are reported. The metal complexes possess tunable spectral bands and exhibit different emission properties depending on the mode of metal coordination.

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π-Extended Dipyrrins Capable of Highly Fluorogenic Complexation with Metal Ions

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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Max Schubert

Papers

Synthetische Versuche mit Blutfarbstoff‐Spaltprodukten und Komplexsalz‐Bildung bei Dipyrryl‐methenen (II.)

Einige Umsetzungen des 2.4‐Dimethyl‐pyrrols

Über Tetrapyrryl‐äthane (I.)