Doping Sumanene with Both Chalcogens and Phosphorus(V): One‐Step Synthesis, Coordination, and Selective Response Toward AgI. (14th February 2019)

• Record Type: Journal Article
• Authors: Wang, Shitao; Yan, Chaoxian; Shang, Jihai; Wang, Wenbo; Yuan, Chengshan; Zhang, Hao‐Li; Shao, Xiangfeng
• Is Part Of: Angewandte Chemie. Volume 131:Number 12(2019)
• Page Start: 3859
• Page End: 3863
• Publication Date: 2019-02-14
• Subjects: Chalkogene -- Heterasumanen -- Phosphole -- Sensoren -- Silber; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.201813070
• Languages: English
• ISSNs: 0044-8249

Abstract

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 . Abstract : Chalkogenatome (S, Se und Te) und Phosphor(V) wurden im konjugierten Gerüst von Sumanen eingebettet. Hieraus ergeben sich neue Funktionen, zum einen als empfindliche Ag + ‐Sonde (X=S) und zum anderen für den Aufbau einer organisch‐anorganischen Interkalationsstruktur mit Kation‐π‐Wechselwirkungen (X=Te).