Boron dipyrromethene (Bodipy) is one of the most extensively investigated organic chromophores. Most of the investigations are focused on the singlet excited state of Bodipy, such as fluorescence. In stark contrast, the study of the triplet excited state of Bodipy is limited, but it is an emerging area, since the triplet state of Bodipy is tremendously important for several areas, such as the fundamental photochemistry study, photodynamic therapy (PDT), photocatalysis and triplet–triplet annihilation (TTA) upconversion. The recent developments in the study of the production, modulation and application of the triplet excited state of Bodipy are discussed in this review article. The formation of the triplet state of Bodipy upon photoexcitation, via the well known approach such as the heavy atom effect (including I, Br, Ru, Ir, etc.), and the new methods, such as using a spin converter (e.g. C60), charge recombination, exciton coupling and the doubly substituted excited state, are summarized. All the Bodipy-based triplet photosensitizers show strong absorption of visible or near IR light and the long-lived triplet excited state, which are important for the application of the triplet excited state in PDT or photocatalysis. Moreover, the methods for switching (or modulation) of the triplet excited state of Bodipy were discussed, such as those based on the photo-induced electron transfer (PET), by controlling the competing Forster-resonance-energy-transfer (FRET), or the intermolecular charge transfer (ICT). Controlling the triplet excited state will give functional molecules such as activatable PDT reagents or molecular devices. It is worth noting that switching of the singlet excited state and the triplet state of Bodipy may follow different principles. Application of the triplet excited state of Bodipy in PDT, hydrogen (H2) production, photoredox catalytic organic reactions and TTA upconversion were discussed. The challenges and the opportunities in these areas were briefly discussed.

The triplet excited state of Bodipy: formation, modulation and application

Red to near-infrared organometallic phosphorescent dyes for OLED applications

Luminescent metal complexes have found increasing use in multiple areas of science and technology, including in chemosensing, light-emitting devices and photochemistry. In particular, the use of cyclometalated iridium(III) complexes as chemosensors has received increasing attention in the recent literature. Phosphorescent metal complexes enjoy a number of advantages (e.g., long-lived phosphorescence, high quantum efficiency and modular syntheses) that render them as suitable alternatives to organic dyes for sensing a variety of analytes. This review describes recent examples of cyclometalated iridium(III) complexes that act as luminescent chemosensors for cations, anions or small molecules.

https://pubs.rsc.org/en/content/articlepdf/2017/sc/c6sc04175b

Luminescent chemosensors by using cyclometalated iridium(iii) complexes and their applications.

Adverse influences of mercury on living organisms are well known. Despite efforts from various regulatory agencies, the build-up of Hg2+ concentration in the environment is of serious concern. This necessitates the search for new and efficient reagents for recognition and detection of Hg2+ in environmental samples as well as for application in diagnostics. Among various detection processes adopted for designing such reagents, generally methodologies that allow associated changes in spectra properties are preferred for the obvious ease in the detection process. Significant changes in the electronic spectral pattern in the visible region of the spectrum also induce detectable changes in solution colour for naked-eye detection and are useful for developing reagents for in-field sample analysis with yes–no type binary responses. However, reagents that allow detection of Hg2+ with associated fluorescence on response are useful for detection of Hg2+ in environmental samples, as well as for use as an imaging reagent, for detection of cellular uptake. High spin–orbit coupling constant for Hg2+ along with its high solvation energy in aqueous medium poses a challenge in developing efficient reagents with fluorescence on response that work in aqueous medium/physiological condition. To get around this problem, several methodologies, like conversion of rhodamine derivative spirolactam to strongly fluorescent xanthenes that form on binding to Hg2+, chemodosimetric reaction for generation of a new luminescent derivative, have been adopted. Apart from these, modified charge transfer processes on binding to Hg2+ have also been utilized for designing reagents for optical detection of Hg2+. Immobilization of such reagents on solid surfaces also led to the development of self-indicating Hg2+ ion scavengers. All such examples are discussed in the present review.

An overview of the recent developments on Hg2+ recognition

New benzoimidazoles (bi) have been synthesized. These compounds readily undergo cyclometalation with iridium trichloride, and bis-cyclometalated iridium complexes, (bi)2Ir(acac) (bi = cyclometalated benzoimidazole; acac = acetylacetonate), can be isolated. One of the complexes, (fbi)2Ir(acac) (fbi = 2-(9,9-diethyl-9H-fluoren-2-yl-1H-benzoimidazole), was also characterized by single-crystal X-ray structural determination. Some of the complexes, (bi)2Ir(acac), are highly phosphorescent at ambient condition. Light-emitting devices using these complexes as dopants were fabricated, and the emission colors range from green to red. Some green- and yellow-emitting devices exhibit very high efficiencies.

含benzoimidazole 配位基的銥金屬高效能磷光材料;Highly Phosphorescent Bis-Cyclometalated Iridium Complexes Containing Benzoimidazole-Based Ligands

Highly efficient orange and red organic light-emitting diodes with iridium(III) complexes bearing benzothiazole cyclometallate ligands as emitters

/pdf/synthesis-and-characterization-of-new-solution-processable-36yht2rqn0.pdf

Synthesis and Characterization of New Solution-Processable Red Iridium (III) Complexes Based on a Phenylation Strategy

Red light organic electroluminescent phosphorescent iridium compound

Small molecular neutral microcrystalline iridium(III) complexes as promising molecular oxygen sensors.

By introducing a phenyl substituent into the meta-site of the phenyl segment of the 2-phenylbenzothiazole ligand, two novel orange iridium(III) complexes, namely, (3Phbt)222Ir(acac) and (3OMePhbt)222Ir(acac), have been synthesized. Compared with their parent compound (bt)222Ir(acac), both of them possess much enhanced thermostability and film amorphism, making them suitable candidates as guests for high performance solution-processed phosphorescent organic light-emitting diodes (PhOLEDs). However, (4Phbt)222Ir(acac) bearing para-phenyl possesses worse processability relative to (bt)222Ir(acac) due to spontaneous crystallization stemming from the intense intermolecular interactions. Single-layer solution-processed PhOLEDs with (3Phbt)222Ir(acac) and (3OMePhbt)222Ir(acac) as guests show peak current efficiency of 17.2 cd A−1 and 15.2 cd A−1, and maximum brightness of 28 270 cd m−2 and 27 900 cd m−2, respectively. Both are greatly improved compared to the devices employing (bt)222Ir(acac) (10.2 cd A−1 and 14 350 cd m−2) and (4Phbt)222Ir(acac) (5.0 cd A−1 and 13 790 cd m−2) as phosphors. Moreover, quite low efficiency roll-off is acquired in these devices at high luminance. The much improved electroluminescence performances of these objective complexes could be mainly attributed to the presence of a rigid phenyl on the appropriate substitution site of the cyclometallate ligand, which leads to improved thermostability with compatible alleviated intermolecular interactions, and consequently enhanced film amorphism.

Iridium(III) complexes with enhanced film amorphism as guests for efficient orange solution-processed single-layer PhOLEDs with low efficiency roll-off.

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