Photoluminescent diamino-substituted dinaphthopentalenes were synthesized successfully by the treatment of in situ prepared dinaphthocyclooctadiyne with lithium amide. This reaction involves a series of transformations including the nucleophilic addition of the lithium amide to a triple bond of the cyclooctadiyne moiety, transannulation, protonation of the resulting pentalene anion, and the nucleophilic substitution of the pentalene core with the lithium amide. In this procedure, a novel double amination step plays a key role. When the diamino-substituted dinaphthopentalenes were irradiated with UV light in toluene, fluorescence was observed at around 580 nm (ΦF < 0.03).
The reaction of an oxygen-and sulfur-bridged incomplete cubane-type molybdenum complex [Mo 3 (¯3-S)(¯-S) 2 (¯-O)-(dtp) 3 (¯-dtp)(CH 3 CN)] (3) (dtp, diethyl dithiophosphate) with methyl propiolate (HC¸CCOOCH 3 , MP) and phenyl acetylene (HC¸CC 6 H 5 , PA) yields trinuclear mixed-valence Mo 3 (IV, V,] (2aMP and 2bMP (a geometrical isomer of 2aMP)) and [Mo 2 (O) 2 (¯-S)(¯-SCH=C(C 6 H 5 )S)(dtp) 2 ] (2aPA and 2bPA (a geometrical isomer of 2aPA)), respectively. The origin of the geometrical isomerism of the dimers comes from the unsymmetric nature of the acetylene derivatives. All of the structures were determined by X-ray crystallography, which revealed that each complex has two carbon-sulfur (¯-S) bonds arising from the adduct formation reaction between complex 3 and an acetylene derivative MP or PA.1 H NMR spectroscopy has proven that the dinuclear complexes are formed via the trinuclear complexes. The XPS spectra of 3MP show that the peaks of Mo 3d 3/2 and Mo 3d 5/2 are clearly split into two in the ratio of two to one, respectively, while those of 3 show no splitting, which indicates that 3MP is a mixed-valence complex with Mo 3 (IV, V, V) oxidation states. Cyclic voltammograms of 3MP and 3PA show chemically reversible one-electron oxidation processes at E 1/2 = 0.21 V and E 1/2 = 0.15 V vs. Ag/Ag + , respectively, and irreversible reduction peaks at ¹0.92 V and ¹1.00 V vs. Ag/Ag + , respectively. The dinuclear complexes, especially 2aPA and 2bPA having phenyl groups, are photosensitive to give their isomeric counter parts.
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