Smart responsive phosphorescent materials for data recording and security protection

Abstract

Smart luminescent materials that are responsive to external stimuli have received considerable interest. Here we report ionic iridium (III) complexes simultaneously exhibiting mechanochromic, vapochromic and electrochromic phosphorescence. These complexes share the same phosphorescent iridium (III) cation with a N-H moiety in the N^N ligand and contain different anions, including hexafluorophosphate, tetrafluoroborate, iodide, bromide and chloride. The anionic counterions cause a variation in the emission colours of the complexes from yellow to green by forming hydrogen bonds with the N-H proton. The electronic effect of the N-H moiety is sensitive towards mechanical grinding, solvent vapour and electric field, resulting in mechanochromic, vapochromic and electrochromic phosphorescence. On the basis of these findings, we construct a data-recording device and demonstrate data encryption and decryption via fluorescence lifetime imaging and time-gated luminescence imaging techniques. Our results suggest that rationally designed phosphorescent complexes may be promising candidates for advanced data recording and security protection. D ata recording, storage and security technologies have been widely utilized in economic and military fields as well as in our daily life. Smart luminescent materials that are responsive to external stimuli have received considerable attention in the construction of optical data recording and storage devices [1][2][3][4][5] . These materials have been classified on the basis of the types of external stimuli that they are responsive to. Mechanochromic materials show changes in emission colour in the presence of mechanical stimuli (for example, shearing, grinding and rubbing) because of the interruption of intermolecular interactions (for example, p-p stacking and hydrogen bonds) [6][7][8][9][10] . Vapochromic luminescence has been observed in materials that are responsive to volatile organic compounds 11,12 . Electric field is an important external stimulus. Electrochromism occurs in p-conjugated polymers because of the reversible transition between two redox states [13][14][15][16] . However, materials showing electrochromic luminescence, which is distinct luminescence colour responses to an electric field, are scarce. We envision the potential commercial applications of electrochromic luminescent materials because they can be conveniently integrated into semiconductor-based electronic devices. In addition, it is conceivable that compounds simultaneously showing mechanochromic, vapochromic and electrochromic luminescence are of great use to the development of multifunctional materials.Phosphorescent transition-metal complexes, such as those of Ir(III) and Pt(II), have been extensively studied for various photonic and electronic applications because of their rich excited-state properties, including high luminescence quantum yields, long emission lifetimes, large Stokes shifts, high photostability and various luminescence colours [17][18][19][20] . These complexes have also been utilized a...

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Reversible Mechanochromic Delayed Fluorescence in 2D Metal–Organic Micro/Nanosheets: Switching Singlet–Triplet States through Transformation between Exciplex and Excimer

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