A charge‐separation‐type ionic solid composed of hexanuclear complexes with a macrocyclic tetragold(I) metalloligand

The reaction of Na[Co III ( d ‐ebp)] ( d ‐H 4 ebp = N , N ′‐ethylenebis[ d ‐penicillamine]) with [(Au I Cl) 2 (dppe)] (dppe = 1,2‐bis[diphenylphosphino]ethane) gave a cationic Au I 4 Co III 2 hexanuclear complex, [Co III 2 (L Au4 )] 2+ ([ 1 ] 2+ ), where [L Au4 ] 4− is a cyclic tetragold(I) metalloligand with a 32‐membered ring, [Au I 4 (dppe) 2 ( d ‐ebp) 2 ] 4− . Complex [ 1 ] 2+ crystallized with NO 3 − to produce a charge‐separation (CS)‐type ionic solid of [ 1 ](NO 3 ) 2 . In [ 1 ](NO 3 ) 2 , the complex cations are assembled to form cationic supramolecular hexamers of {[ 1 ] 2+ } 6 , which are closely packed in a face‐centered cubic (fcc) lattice structure. The nitrate anions of [ 1 ](NO 3 ) 2 were accommodated in hydrophilic and hydrophobic tetrahedral interstices of the fcc structure to form tetrameric and hexameric nitrate clusters of {NO 3 − } 4 and {NO 3 − } 6 , respectively. An analogous CS‐type ionic solid formulated as [Ni II Co III (L Au4 )](NO 3 ) ([ 2 ](NO 3 )) was obtained when a 1:1 mixture of Na[Co III ( d ‐ebp)] and [Ni II ( d ‐H 2 ebp)] was reacted with [(Au I Cl) 2 (dppe)], accompanied by the conversion of the diamagnetic, square‐planar [Ni II ( d ‐H 2 ebp)] to the paramagnetic, octahedral [Ni II ( d ‐ebp)] 2− . While the overall fcc structure in [ 2 ](NO 3 ) was similar to that of [ 1 ](NO 3 ) 2 , none of the nitrate anions were accommodated in any hydrophobic tetrahedral interstice, reflecting the difference in the complex charges between [ 1 ] 2+ and [ 2 ] + .