Doping Sumanene with Both Chalcogens and Phosphorus(V): One-Step Synthesis, Coordination, and Selective Response Toward Ag-I

摘要

Heterasumanenes 4-6 containing chalcogen (S, Se, and Te) and phosphorus atoms have been synthesized in a onepot reaction from trichalcogenasumanenes 1-3 by replacing one chalcogen atom with a P=S unit. The P=S unit makes 4-6 almost planar and shrinks the HOMO-LUMO gap as compared to 1-3. The bonding between Ag+ and S atom on P=S brings about a distinct change to the optical properties of 4-6; 4 in particular shows a selective fluorescence response toward Ag+ with LOD of 0.21 mu m. Compounds 4-6 form complexes with AgNO3 to be (4)(2)center dot AgNO3, (5)(2)center dot AgNO3, and (6) (2)center dot(AgNO3)(3). In complexes, the coordination between Ag( )(+)and P=S is observed, which leads to shrinkage of C-P and C- X (X= S, Se, Te) bond lengths. As a result, 4, 5, and 6 are all bowl-shaped in complexes with bowl-depths reaching to 0.66 angstrom, 0.42 angstrom, and 0.40 angstrom, respectively. There are Ag-Te dative bonds between Ag+ and Te atom on telluorophene in (6)(2)center dot(AgNO3)(3).