Two new isolated Zn-ε-Keggin clusters modified by conjugated organic ligands with decent electrocatalytic and third-order NLO properties

Two new bifunctional isolated hybrid compounds, [ε-PMoV8MoVI4O 37 (OH) 3 Zn 4 ][iql] 4 ·6H 2 O ( 1 ) and [ε-PMoV8MoVI4O 38 (OH) 2 Zn 4 ][bipy] 3 [(CH 3 COO)(bipy) 2 Zn]·2H 2 O ( 2 ) (where iql = isoquinoline and bipy = 2,2′-bipyridine), based on Zn-ε-Keggin were successfully synthesized by self-assembly under hydrothermal conditions. It is interesting to note that acetate in 2 acted as a linker connecting the ε-Keggin anion with the one Zn atom (Zn5) and enabled the ε-Keggin anion to coordinate with more bipy ligands, culminating with a larger isolated system, which is the first reported isolated cluster of Zn 5 PMo 12 . Meanwhile, compounds 1–2 show great electrochemical behaviors and excellent electrocatalytic activity for the degradation of NaNO 2 . In addition, compound 2 displays better third-order NLO performance than 1 due to the presence of more conjugated rings, with a TPA cross section ( σ ) of 1819 GM, which suggests that compound 2 has the potential to function as a bifunctional material with tremendous prospects.