Molecular Rearrangement of Trinuclear Cu(I)‐NHC: Synthesis of Mono, Binuclear and Polymeric Cu(I)‐NHCs

A trinuclear Cu(I)‐NHC [Cu 3 (py 2 im) 3 ](PF 6 ) 3 ( 1 ) has been synthesized in a very short period of time (5‐10 min) in multi‐gram scale using less expensive Cu(OAc) 2 ⋅H 2 O and py 2 imH⋅PF 6 in presence of L‐ascorbic acid in CH 3 OH under aerobic conditions at room temperature. Further, a very facile synthetic route has been developed to obtain a mononuclear [Cu(py 2 im)(phen)](PF 6 ) ( 3 ), binuclear [Cu 2 (py 2 im) 3 ](PF 6 ) 2 ( 2 ) and 1D polymeric chain of Cu(I)‐NHC {[Cu(py 2 im)(4,4′‐bpy)](PF 6 )} n ( 4 ), {[Cu(py 2 im)(bpe)](PF 6 )} n ( 5 ), {[Cu(py 2 im)(bpe)](PF 6 )} n . {[Cu 2 (py 2 im) 3 ](PF 6 )} n ( 6 ) and {[Cu(py 2 im)(azpy)](PF 6 )} n ( 7 ) from a trinuclear Cu(I)‐NHC cluster ( 1 ) using additional linear bridging co‐ligands such as 4,4′‐bipyridine (bpy), trans‐1,2‐bis(4‐pyridyl)ethene (bpe), 4,4′‐azobispyridine (azpy) etc. In CH 3 CN, 4 and 5 were rearranged to adamantanoid core 3D Cu(I)‐MOF {[Cu(bpy) 2 ](PF 6 )} n ( 8 ) and {[Cu(bpe) 2 ](PF 6 )} n ( 9 ), respectively. X‐ray crystallographic structure of 6 exhibits two molecules of 2 which was trapped between two polymeric chains.