A novel amino-benzothiadiazole bearing diphenylphosphine groups (L) was designed and synthesized. A number of its coordination compounds of Cu(I) (1•0.75C 7 H 8 , 2a,b), Pd(II) (4), and Pt(II) (5) were prepared demonstrating the coordination of L ligand via N and/or P atoms. The reaction with strong Lewis acid Zn(II) resulted in the rearrangement of PNP to P−P−N moiety and formation of complex 3. The structures of L, 2−5 were determined by single crystal X-ray (XRD) diffraction, while that of 1•0.75C 7 H 8 was determined by powder XRD analysis. Intermolecular secondary bonding of S•••S interactions in the compounds, unusual for benzothiadiazoles, was discussed supported by quantum chemical calculations. Differences in the structures of the compounds cause significant changes of photophysical properties. In particular, the position of the electronic absorption band is featured by the conformation of L, viz., the dihedral angle between the benzothiadiazole unit and the PNP moiety, as proved by TD-DFT calculations performed on model molecules. The photophysical properties of the compounds also strongly depend on the coordination mode of L: the presence of a bond between the metal and the N atom of the thiadiazole unit plays an essential role in defining the position of the absorption and emission bands as well as emission lifetime of these compounds. The thermally activated delayed fluorescence and phosphorescence mechanisms in a thermal equilibrium were determined for 1• 0.75C 7 H 8 . Complex 5 features a broad emission band spanning the entire visible region; moreover, it shows an unusual clear-white luminescence, which remains visible even in the daylight.
Exploring pure organic single-component materials featuring room-temperature phosphorescence and excitation-dependent color-tunability attracts great attention in recent years. Such challenging materials are highly demanded for the OLED industry and are very...
Here we describe the synthesis of a novel N,N’-bis(2,1,3-benzothiadiazol-4-yl)-1-phenylphosphanediamine (H2L) and its zinc (II) and copper (I) coordination compounds [Zn2L2]·nC7H8 (1·nC7H8), [Zn2(H2L)2Cl4]·nC7H8 (2·nC7H8), and [Cu(H2L)Cl]n·nTHF (3·THF). According to single crystal X-ray diffraction analysis, H2L ligand and its deprotonated species exhibit different coordination modes. An interesting isomerism is observed for the complexes [Zn2(H2L)2Cl4] (2a and 2b) that differ by the arrangement of H2L. Both complexes possess internal cavities capable of incorporating toluene molecules. Upon toluene release, the geometry of 2b changes substantially, while that of 2a changes slightly. Due to the diverse structures, the compounds 1–3 reveal different photophysical properties. These results are discussed based on previously reported studies and DFT (density functional theory) calculations.
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