Chiral {Ni 6 PW 9 } Cluster-Organic Framework: Synthesis, Structure, and Properties.

A chiral three-dimensional polyoxometalate cluster-organic framework (POMCOF) H 3 [(btc)Ni 6 (μ 3 -OH) 3 (H 2 O) 5 (B-α-PW 9 O 34 )]·17H 2 O ( 1 , btc = 1,2,4-benzenetricarboxylate) has been made under hydrothermal conditions in the absence of amine or chiral starting reagents. 1 shows high stability in CH 3 CN/DMF (1:3), acidic, and basic solutions with the pH ranging from 2 to 12 for 5 days. The UV-vis reflectance spectra and Mott-Schottky measurements reveal that 1 could be a suitable catalyst for photocatalysis. Visible-light-driven H 2 evolution studies have demonstrated that 1 is an ecofriendly, efficient, and recyclable catalyst with a H 2 evolution rate of 1058.24 μmol h -1 g -1 . Nonlinear optical (NLO) measurement reveals that 1 exhibits a second-harmonic generation (SHG) response of about 1.4 times that of KH 2 PO 4 (KDP), indicating that 1 is a potential NLO material as well.