light-emitting device (OLED) in 1998, [1] phosphorescent transition-metal complexes, especially for noble metal-based ones (e.g., iridium(III), platinum(II), etc.) as triplet emitters toward highly efficient organic electroluminescence, have aroused extensive attention. [15-21] Owing to strong spin-orbit coupling effect, these complexes may use both singlet and triplet excitons to greatly enhance the efficiency of OLED, breaking the upper limit of the conventional fluorescent device efficiency. Due to their unique properties of excited states, they also have extended their applications in other fields, for instance, catalysis, organic solar cells, organic memory devices, biological sensing and imaging, photodynamic therapy, information recording, and security protection, etc. [22-27] Although extensive works have been done to the design and preparation of phosphorescent materials based on noble metals, these noble metals usually have some disadvantages (such as high cost and low abundance in nature), thereby limiting their practical applications. The relatively abundant and cheap PTMCs of low toxicity have drawn considerable interests very recently. [4,23,24,28-31] Many kinds of non-noble metal-based PTMCs such as copper(I), tungsten(VI), and manganese(II) complexes have emerged rapidly. [4,23-25,28-31] Phosphorescent manganese(II) complexes show great potentials in many applications, due to their features including highly efficient phosphorescence, flexible design in molecular structure, ease of synthesis, and rich physical properties (e.g., triboluminescence, stimuli-responsivity, etc.). [24,25a,32-36] Compared with the noble metals, manganese element with an atomic number of 25 has abundant reserves, is environmentally friendly and inexpensive. Moreover, it has richer valence and coordination mode, which has been widely used in the fields of catalysis, ferroelectric, and magnetic materials. [37-39] Among the various valence states of manganese ion, the divalent manganese ion having a 3d 5 electron configuration has a 4 T 1 − 6 A 1 radiative transition closely related to the crystal field strength. The crystal field strength in the metal complex highly depends on the chemical structure of the ligand and the coordination number. These features make the manganese(II) complexes having rich photophysical properties. By regulating the ligand structure, the organic counterion and the coordination number of the manganese(II) complex, the green, yellow, orange, red, or even near-infrared phosphorescence can be achieved. [23-25,36,40] It Phosphorescent manganese(II) complexes are emerging as a new generation of phosphorescent materials showing great potentials in many applications, owing to their unique features including highly efficient phosphorescence, diverse structural/molecular design, and ease of synthesis, structural diversity, rich physical properties (e.g., triboluminescence, stimuli-responsivity, etc.), high abundance, and low cost. The research on phosphorescent manganese(II) complexes is just in its infancy...

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