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

Heterasumanenes 4-6 containing chalcogen (S, Se, and Te) and phosphorus atoms have been synthesized in a one-pot 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 μm. Compounds 4-6 form complexes with AgNO to be (4) ⋅AgNO , (5) ⋅AgNO , and (6) ⋅(AgNO ) . 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 Å, 0.42 Å, and 0.40 Å, respectively. There are Ag-Te dative bonds between Ag and Te atom on telluorophene in (6) ⋅(AgNO ) .