Odd-numbered and high-nuclearity coordination clusters are extremely rare,yet they represent an intriguing subclass lacking regular repeating building blocks and high structural symmetry for understanding self-assembl...Odd-numbered and high-nuclearity coordination clusters are extremely rare,yet they represent an intriguing subclass lacking regular repeating building blocks and high structural symmetry for understanding self-assembled multiatomic systems.Herein,the largest cobalt and polydentate ligand based cluster featuring odd-nuclearity,namely[Co_(19)(HL1)_(8)(L1)_(12)(L′)_(2)(Ac)_(4)]·10CH_(3)CH_(2)OH·6H_(2)O(1,H_(2)L1=1H-benzo[d]imidazole-2-yl)methanol,HL'=1H-benzo[d]imidazole),was obtained with in-situ ligand transformation from H_(2)L1 to L′.It features a hierarchical trilayer and void-cage inside structure,consisting of central disc-shaped[Co_(7)L_(10)]core with two[Co_(6)]rings on both sides.ESI-MS of crystal 1 yields a series of more than sixteen fragments,all featuring an integrated[Co_(19)]core,suggesting stability of the polynuclear cluster in solution.During increased in-source energy from 0 to 100 eV,all MS peaks shifted to a lower m/z range,but the[Co_(19)]core remained intact,excepting for the stepwise elimination of up to three Ac^(−)anions or three L1 linkers.PXRD tracking of the reaction sediments showed the formation of a key precursor of[Co_(4)L_(4)]cubane at 3 h,and its content decreased at 6 h and vanished at 12 h,followed by the appearance of crystals 1 by the generation of a clear solution at 18 h,suggesting an initial cluster assembly-disassembly process.ESI-MS spectra analysis of both reaction sediment and solution further identify the existence of other crucial higher-nuclearity reassembled fragments of[Co_(7)L_(10)]disk and its expansion of[Co_(13)L_(12)(L′)_(2)].A probable tandem assembly-disassembly-reassembly mechanism is put forward as[CoL_(2)]→[Co_(4)L_(4)]→[Co_(7)L_(10)]→[Co_(13)L_(12)(L′)_(2)]→[Co_(19)L_(2)0(L′)_(2)].Their evolution also indicated the ingenious synergy of coexisting organic,inorganic and in-situ generated ligands,along with diverse coordination geometries of metal ions,plays a directional role in forming odd-numbered and high-nuclearity coordination clusters.Magnetism analysis revealed antiferromagnetic coupling plays dominated role in the cluster.展开更多
基金supported by the BAGUI Talent Program in Guangxi Province(No.2019AC26001)the National Natural Science Foundation of China(Nos.22171075,U23A2080,22371173).
文摘Odd-numbered and high-nuclearity coordination clusters are extremely rare,yet they represent an intriguing subclass lacking regular repeating building blocks and high structural symmetry for understanding self-assembled multiatomic systems.Herein,the largest cobalt and polydentate ligand based cluster featuring odd-nuclearity,namely[Co_(19)(HL1)_(8)(L1)_(12)(L′)_(2)(Ac)_(4)]·10CH_(3)CH_(2)OH·6H_(2)O(1,H_(2)L1=1H-benzo[d]imidazole-2-yl)methanol,HL'=1H-benzo[d]imidazole),was obtained with in-situ ligand transformation from H_(2)L1 to L′.It features a hierarchical trilayer and void-cage inside structure,consisting of central disc-shaped[Co_(7)L_(10)]core with two[Co_(6)]rings on both sides.ESI-MS of crystal 1 yields a series of more than sixteen fragments,all featuring an integrated[Co_(19)]core,suggesting stability of the polynuclear cluster in solution.During increased in-source energy from 0 to 100 eV,all MS peaks shifted to a lower m/z range,but the[Co_(19)]core remained intact,excepting for the stepwise elimination of up to three Ac^(−)anions or three L1 linkers.PXRD tracking of the reaction sediments showed the formation of a key precursor of[Co_(4)L_(4)]cubane at 3 h,and its content decreased at 6 h and vanished at 12 h,followed by the appearance of crystals 1 by the generation of a clear solution at 18 h,suggesting an initial cluster assembly-disassembly process.ESI-MS spectra analysis of both reaction sediment and solution further identify the existence of other crucial higher-nuclearity reassembled fragments of[Co_(7)L_(10)]disk and its expansion of[Co_(13)L_(12)(L′)_(2)].A probable tandem assembly-disassembly-reassembly mechanism is put forward as[CoL_(2)]→[Co_(4)L_(4)]→[Co_(7)L_(10)]→[Co_(13)L_(12)(L′)_(2)]→[Co_(19)L_(2)0(L′)_(2)].Their evolution also indicated the ingenious synergy of coexisting organic,inorganic and in-situ generated ligands,along with diverse coordination geometries of metal ions,plays a directional role in forming odd-numbered and high-nuclearity coordination clusters.Magnetism analysis revealed antiferromagnetic coupling plays dominated role in the cluster.
