Doping Sumanene with Both Chalcogens and Phosphorus(V): One‐Step Synthesis, Coordination, and Selective Response Toward AgI

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Abstract 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 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, 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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