Doping Sumanene with Both Chalcogens 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 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 μ m . Compounds 4 – 6 form complexes with AgNO 3 to be ( 4 ) 2 ⋅AgNO 3 , ( 5 ) 2 ⋅AgNO 3 , and ( 6 ) 2 ⋅(AgNO 3 ) 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 ⋅(AgNO 3 ) 3 .