A charge‐separation‐type ionic solid composed of hexanuclear complexes with a macrocyclic tetragold(I) metalloligand. Issue 12 (1st June 2020)

• Record Type: Journal Article
• Authors: Pratikha, Rycce S.; Inoue, Takahiro; Arai, Yuka; Kojima, Tatsuhiro; Yoshinari, Nobuto; Konno, Takumi
• Is Part Of: Journal of the Chinese Chemical Society. Volume 67:Issue 12(2020)
• Page Start: 2189
• Page End: 2197
• Publication Date: 2020-06-01
• Subjects: crystal structure -- heterometallic complexes -- ionic solid -- ligand modification -- metalloligand; Chemistry -- Periodicals; Electronic journals; 540.5
• DOI: 10.1002/jccs.202000163
• Languages: English
• ISSNs: 0009-4536

Abstract

Abstract: The reaction of Na[Co III (d ‐ebp)] (d ‐H4 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 NO3 − to produce a charge‐separation (CS)‐type ionic solid of [1 ](NO3 )2 . In [1 ](NO3 )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 ](NO3 )2 were accommodated in hydrophilic and hydrophobic tetrahedral interstices of the fcc structure to form tetrameric and hexameric nitrate clusters of {NO3 − }4 and {NO3 − }6, respectively. An analogous CS‐type ionic solid formulated as [Ni II Co III (L Au4 )](NO3 ) ([2 ](NO3 )) was obtained when a 1:1 mixture of Na[Co III (d ‐ebp)] and [Ni II (d ‐H2 ebp)] was reacted with [(Au I Cl)2 (dppe)], accompanied by the conversion of the diamagnetic, square‐planar [Ni II (d ‐H2 ebp)] to the paramagnetic, octahedral [Ni II (d ‐ebp)] 2− . While the overall fcc structure in [2 ](NO3 ) was similar to that of [1 ](NO3 )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 ] + . Abstract : A cationic Au I 4 Co III 2 complex ([1 ] 2+ ) containing Co III centers that are surrounded by a tetragold(I) metalloligand with a 32‐membered ring was newly synthesized. [1 ] 2+ crystallized with NO3 − to construct a CS‐type ionic solid, in which cations of [1 ] 2+ are assembled in supramolecular hexamers that are closely packed in a fcc lattice structure. An analogous CS‐type ionic solid containing both Ni II and Co III centers is also reported.