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Here we describe the synthesis of a novel N,N'-bis(2,1,3-benzothiadiazol-4-yl)-1-phenylphosphanediamine (H 2 L) and its zinc (II) and copper (I) coordination compounds [Zn 2 L 2 ]·nC 7 H 8 ( 1 ·nC 7 H 8 ), [Zn 2 (H 2 L) 2 Cl 4 ]·nC 7 H 8 ( 2 ·nC 7 H 8 ), and [Cu(H 2 L)Cl] n ·nTHF ( 3 ·THF). According to single crystal X-ray diffraction analysis, H 2 L ligand and its deprotonated species exhibit different coordination modes. An interesting isomerism is observed for the complexes [Zn 2 (H 2 L) 2 Cl 4 ] ( 2a and 2b ) that differ by the arrangement of H 2 L. 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.

Structural and Photophysical Properties of 2,1,3-Benzothiadiazole-Based Phosph(III)azane and Its Complexes