Heterasumanenes 4-6 containing chalcogen (S,S e, and Te)and phosphorus atoms have been synthesized in aonepot reaction from trichalcogenasumanenes 1-3 by replacing one chalcogen atom with aP =Sunit. The P=Sunit makes 4-6 almost planar and shrinks the HOMO-LUMO gap as compared to 1-3.T he bonding between Ag + and Sa tom on P = Sbrings about adistinct change to the optical properties of 4-6; 4 in particular shows as elective fluorescence response towardA g + with LOD of 0.21 mm.C ompounds 4-6 form complexes with AgNO 3 to be (4) 2 ·AgNO 3 ,( 5) 2 ·AgNO 3 ,a nd (6) 2 ·(AgNO 3 ) 3 .I nc omplexes,t he coordination between Ag + and P = Sisobserved, whichleads to shrinkage of C À Pand C À X( X= S, Se,T e) bond lengths.Asaresult, 4, 5,a nd 6 are all bowl-shaped in complexes with bowl-depths reaching to 0.66 ,0 .42 ,a nd 0.40 ,r espectively.T here are AgÀTe dative bonds between Ag + and Te atom on telluorophene in (6) 2 ·(AgNO 3 ) 3 .

Trichalcogenasumanenes containing two kinds of chalcogen are synthesized. The majority chalcogen governs the optical properties and the heavier chalcogen governs the chemical reactivity.

Buckybowls have unique properties that can be tailored by embedding main-group elements into their π-scaffolds. Herein, a synthetic approach is developed for producing monoazadichalcogenasumanenes (4 a/4 b, 6 a/6 b, 7 a/7 b) derived from sumanene by replacing its three benzylic carbons with one nitrogen and two chalcogen atoms (S for 4 a/4 b, Se for 6 a/6 b, Te for 7 a/7 b). Monoazadichalcogenasumanenes are deeper π-bowls than trichalcogensumanenes as the CÀ N bond is much shorter than CÀ X (X = S, Se, Te). The bowl-depth of 4 b (0.95 Å) is greater than that of corannulene (0.85 Å). The nitrogen atom donates electron density to the entire π-system that makes monoazadichalcogenasumanenes electron-rich. They undergo ring reconstruction of chalcogenophene ring via transferring a chalcogen atom from one molecule to another under acidic conditions. The nitrogen and chalcogen atoms play crucial role on this reaction.

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.