Synthesis, Properties, and Complex Formation of Antimony- and Bismuth-Bridged Bipyridyls

Abstract

Antimony-and bismuth-bridged bipyridyls (dipyridinostibole and dipyridinobismole; DPySb and DPyBi) were prepared by the reactions of dilithiobipyridyl with dibromophenylstibine and diiodophenylbismuthine. Xray diffraction studies of the crystal structures revealed a high planarity of the heterole ring. Cyclic voltammograms obtained in acetonitrile indicated enhanced electron affinity in comparison to a bridge-free bipyridyl. These compounds showed weak fluorescence at room temperature and visible phosphorescence at 77 K with emission maxima and lifetimes of λ max = 453 nm and τ = 1.03 ms for DPySb and λ max = 454 nm and τ = 0.26 ms for DPyBi, respectively. Solid-state phosphorescence was also observed from these dipyridinoheteroles at 77 K. Their copper complexes were prepared by interaction with Cu 2 I 2 (PPh 3 ) 3 , which produced red phosphorescence in the solid state at room temperature.

Synthesis, Structural Characterization, and Optical Properties of Benzene-Fused Tetracyclic and Pentacyclic Stiboles

“…The bond lengths and angles around the antimony atom in 5 are approximately the same as in linear stibole 3. Furthermore, similar bond lengths and angles have been observed among previously reported stiboles, including benzostiboles [27,35], dipyridostibole [30], and 7-tolyldinaphthostibole [31]. Table 1.…”

“…Subsequently, they reported both the synthesis of pyridine-fused tricyclic stibole V (9-phenyl-stibolo [2,3c:5,4-c ]dipyridine) and its phosphorescence at low temperature. They also revealed that the copper complex derived from stibole V and Cu 2 I 2 (PPh 3 ) 3 displayed phosphorescence at room temperature [30]. We reported the synthesis and structural study of optically active 7-(p-tolyl)dinaphtho[2,1-b:1 ,2 -d]stibole (7-Tol-DNSb) and revealed the dynamic behavior of the binaphthyl skeleton based on the C 2 symmetry axis [31].…”

Organic Compounds of Bismuth: Synthesis, Structure, and Applications

“…This compound and related antimony derivative (DPySb) possess a weak fluorescence at room temperature and an appreciable phosphorescence at 77 K with the emission maxima at λ max = 453 and 454 nm and the lifetimes τ = 1.03 and 0.26 ms for DPySb and DPyBi, respectively. Solid-phase phosphorescence was also observed for these dipyridinoheterols at 77 K. The reaction of DPyBi with Cu 2 I 2 (PPh 3 ) 3 affords the corresponding copper complex [(PPh 3 )CuI(DPyBi)-CuI(PPh 3 )] 2 , which demonstrates red phosphorescence in the solid state at room temperature [42].…”

Crystal Structures and Phosphorescent Properties of Group 14 Dipyridinometalloles and Their Copper Complexes

“…This is likely due to the intramolecular through space interaction between the two dipyridinometallole units that are linked by Cu 2 I 2 units. [21] For DPyS1À Cu, however, the DPyS1 units linked by Cu 3 I 3 units are too distant from each other to realize similar through space interaction.…”