Abstract
Two unique ZnI -containing MOFs {[ZnI8 ZnII3 (H2 O)x (HL)12 ](OH)2 ⋅13 H2 O}n (x=6, 1; x=2, 2) (HL=tetrazole monoanion) with high-nuclearity Zn-cages were prepared successfully. These Zn-cages are constructed from [ZnI8 ] clusters with multi-centered ZnI -ZnI bonds and ZnII ions. [ZnI8 ] clusters in 1 and 2 display Oh and D4h symmetry, respectively. Importantly, eight [ZnI8 ] clusters and six ZnII ions form a large [Zn70 ] nanocage in 1. To our knowledge, this is the first MOF based on polynuclear Zn-cages consisting of ZnI and ZnII ions. Compared with reported ZnI -species, 1 and 2 display high thermal and solvent stabilities. Theoretical investigations based on DFT calculations uncover that effective 4s-4s orbital overlap and electron delocalization through these a1g +t1u molecular orbitals on [ZnI8 ] clusters lead to considerable aromatic stabilization, which can explain well the intrinsic stability of 1 and 2. Interestingly, 1 can behave as a luminescent probe to detect the toxic CrVI ions in aqueous.
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