Abstract
AbstractA new series of mono‐ and bis‐alkynyl CoIII(TIM) complexes (TIM=2,3,9,10‐tetramethyl‐1,4,8,11‐tetraazacyclotetradeca‐1,3,8,10‐tetraene) is reported herein. The trans‐[Co(TIM)(C2R)Cl]+ complexes were prepared from the reaction between trans‐[Co(TIM)Cl2]PF6 and HC2R (R=tri(isopropyl)silyl or TIPS (1), ‐C6H4‐4‐tBu (2), ‐C6H4‐4‐NO2 (3 a), and N‐mesityl‐1,8‐naphthalimide or NAPMes (4 a)) in the presence of Et3N. The intermediate complexes of the type trans‐[Co(TIM)(C2R)(NCMe)](PF6)(OTf), 3 b and 4 b, were obtained by treating 3 a and 4 a, respectively, with AgOTf in CH3CN. Furthermore, bis‐alkynyl trans‐[Co(TIM)(C2R)2]PF6 complexes, 3 c and 4 c, were generated following a second dehydrohalogenation reaction between 3 b and 4 b, respectively, and the appropriate HC2R in the presence of Et3N. These new complexes have been characterized using X‐ray diffraction (2, 3 a, 4 a, and 4 c), IR, 1H NMR, UV/Vis spectroscopy, fluorescent spectroscopy (4 c), and cyclic voltammetry.
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