Doping Sumanene with both Chalcogen and Phosphorus(V): One‐Step Synthesis, Coordination and Selective Response toward Ag(I)

Heterasumanenes 4‐6 containing chalcogen (S, Se, and Te) and phosphorus atoms have been synthesized in one‐pot from trichalcogenasumanenes 1‐3 by replacing one chalcogen atom with 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 distinct change on optical properties of 4‐6, particularly 4 shows selective fluorescence response toward Ag+ with LOD of 0.21 μM. The 4‐6 form complexes with AgNO3 to be (4)2•AgNO3, (5)2•AgNO3, and (6)2•(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, the 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)2•(AgNO3)3.

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