Two near-UV and visible chromophores of CpCo(Dithiolene) complexes with pyridinium-dicyanomethylide group

摘要: Abstract Tetracyanoethylene oxide (TCNEO) reacted with [CpCo(dithiolene)] (Cp =  η 5 -cyclopentadienyl) complexes having 4-pyridyl or 3-pyridyl group to undergo a dicyanomethylation the nitrogen atom on pyridyl group. The reaction of [CpCo(S 2 C ( 4 Py) )] 1 ) TCNEO formed both monodicyanomethylated Py)( Py–C(CN) ))] 1a and bisdicyanomethylated 1b ). Py))] give 2a but no occurred 2-pyridyl excess form only dicyanomethylated acetylene derivative Py–C C–( 2c ), followed by dissociation CpCoS fragment. n )(2-thienyl))]  = 4 4a 3 5a )) were also prepared from Py)(2-thienyl))] TCNEO. was structurally characterized X-ray diffraction study. all showed dithiolene LMCT absorption in range 605–644 nm e  = 7000–9200 M −1  cm very strong due their pyridinium-dicyanomethylide moieties near-UV region (e.g. : λ max  = 470 nm,  = 43,400 M CV exhibited two reduction waves. first is Co III /Co II second one moiety. reduced − stable enough for several minutes according visible spectroelectrochemical measurement. ESR spectrum indicated eight hyperfine splittings interaction nuclear spin cobalt I  = 7/2).