TY - JOUR
T1 - Enantiomeric Polyoxometalates Based on Malate Chirality-Inducing Tetra-Zr IV -Substituted Keggin Dimeric Clusters
AU - Wang, Yue Lin
AU - Zhao, Jun Wei
AU - Zhang, Zhong
AU - Sun, Jun Jun
AU - Li, Xu Yan
AU - Yang, Bai Feng
AU - Yang, Guo Yu
N1 - Publisher Copyright:
© 2019 American Chemical Society.
PY - 2019/4/1
Y1 - 2019/4/1
N2 - On the basis of the synergistic strategy of lacunary polyoxometalate structure-directing function and chiral ligand inducting role, two pairs of enantiomeric polyoxotungstates, (NH 4 ) 4 (TMA) 4 [Zr 4 (μ 3 -O) 2 (l-/d-mal) 2 (B-α-HSiW 10 O 37 ) 2 ] (TMA = tetramethylammonium, mal = malate (C 4 H 5 O 5 ); l-mal for 1a, d-mal for 1b) and (NH 4 ) 4 (TMA) 4 [Zr 4 (μ 3 -O) 2 (l-/d-mal) 2 (B-α-PW 10 O 37 ) 2 ] (l-mal for 2a, d-mal for 2b), and a mesomeric polyoxotungstate, (NH 4 ) 3 Na 2 K 5 [Zr 4 (μ 3 -O) 2 (l-mal)(d-mal)(B-α-SiW 10 O 37 ) 2 ] (3), were hydrothermally synthesized. 1a, 2a and 1b, 2b respectively exhibit 1-D 2 1 right- and left-hand helical chains formed by hydrogen-bonding interactions, and 3 forms a 3-D (3,10)-connected framework by Na + /K + ions with {4 18 .6 24 .8 3 }{4 3 } 2 topology. These homochiral compounds represent the first examples of enantiomerically pure Zr IV -substituted Keggin POMs. In this system, {Zr 4 (μ 3 -O) 2 (l-/d-mal) 2 } clusters transfer chirality from d- or l-mal to Keggin polyoxotungstate dimeric clusters, which was demonstrated by structural comparison between the homochiral architecture and mesomer as well as circular dichroism spectra of enantiomers. UV-vis diffuse reflectance spectra reveal that 1-3 are potential semiconductor materials. In addition, 1 and 2 exhibit second harmonic generation response with their response intensities of 0.8 times that of KDP.
AB - On the basis of the synergistic strategy of lacunary polyoxometalate structure-directing function and chiral ligand inducting role, two pairs of enantiomeric polyoxotungstates, (NH 4 ) 4 (TMA) 4 [Zr 4 (μ 3 -O) 2 (l-/d-mal) 2 (B-α-HSiW 10 O 37 ) 2 ] (TMA = tetramethylammonium, mal = malate (C 4 H 5 O 5 ); l-mal for 1a, d-mal for 1b) and (NH 4 ) 4 (TMA) 4 [Zr 4 (μ 3 -O) 2 (l-/d-mal) 2 (B-α-PW 10 O 37 ) 2 ] (l-mal for 2a, d-mal for 2b), and a mesomeric polyoxotungstate, (NH 4 ) 3 Na 2 K 5 [Zr 4 (μ 3 -O) 2 (l-mal)(d-mal)(B-α-SiW 10 O 37 ) 2 ] (3), were hydrothermally synthesized. 1a, 2a and 1b, 2b respectively exhibit 1-D 2 1 right- and left-hand helical chains formed by hydrogen-bonding interactions, and 3 forms a 3-D (3,10)-connected framework by Na + /K + ions with {4 18 .6 24 .8 3 }{4 3 } 2 topology. These homochiral compounds represent the first examples of enantiomerically pure Zr IV -substituted Keggin POMs. In this system, {Zr 4 (μ 3 -O) 2 (l-/d-mal) 2 } clusters transfer chirality from d- or l-mal to Keggin polyoxotungstate dimeric clusters, which was demonstrated by structural comparison between the homochiral architecture and mesomer as well as circular dichroism spectra of enantiomers. UV-vis diffuse reflectance spectra reveal that 1-3 are potential semiconductor materials. In addition, 1 and 2 exhibit second harmonic generation response with their response intensities of 0.8 times that of KDP.
UR - http://www.scopus.com/inward/record.url?scp=85063510613&partnerID=8YFLogxK
U2 - 10.1021/acs.inorgchem.9b00258
DO - 10.1021/acs.inorgchem.9b00258
M3 - Article
C2 - 30882216
AN - SCOPUS:85063510613
SN - 0020-1669
VL - 58
SP - 4657
EP - 4664
JO - Inorganic Chemistry
JF - Inorganic Chemistry
IS - 7
ER -