The First Organic-inorganic Hybrid Compound Based on Polyoxotungstates and Alkali-tris(imidazolyl) Segments with Electrocatalytic Activity
Wanli Zhou1 · Yanping Zheng1 · Jun Peng2
1 Faculty of Chemistry, Tonghua Normal University, Tonghua, Jilin, 134002, PR China E-mail:
2 Key Laboratory of Polyoxometalate Science of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Changchun, Jilin, 130024, PR China
Electronic Supplementary Information
Table S1. Selected bond lengths (Å) and angles (°) for compound 1.
W(1)-O(16)W(1)-O(15)
W(1)-O(7)
W(1)-O(17)
W(1)-O(12)
W(1)-O(19)
W(1)-O(3)
W(2)-O(21)
W(2)-O(8)
W(2)-O(13)
W(2)-O(11)
W(2)-O(15)
W(2)-O(4)
W(2)-O(3)
W(3)-O(22)
W(3)-O(5)
W(3)-O(6)
W(3)-O(9)
W(3)-O(7)
W(3)-O(14)
W(3)-O(19)
W(4)-O(18)
W(4)-O(17)
C(1)-C(2)
O(16)-W(1)-O(15)
O(15)-W(1)-O(17)
O(12)-W(2)-O(3)
O(8)-W(2)-O(4) / 1.698(12)
1.836(13)
1.862(15)
1.875(14)
1.904(13)
2.33(2)
2.40(5)
1.668(12)
1.840(15)
1.868(13)
1.901(15)
1.924(13)
2.37(2)
2.41(5)
1.669(13)
1.838(15)
1.880(14)
1.890(13)
1.911(15)
2.36(2)
2.43(2)
1.666(13)
1.868(14)
1.35(2)
100.1(7)
87.0(6)
93.9(13)
95.8.5(8) / W(4)-O(8)
W(4)-O(3)
W(5)-O(20)
W(5)-O(10)
W(5)-O(6)
W(5)-O(19)
W(5)-O(8)
W(6)-O(2)
W(6)-O(9)
W(6)-O(11)
W(6)-O(1)
W(6)-O(14)
W(6)-O(4)
Na(1)-N(5)
Na(1)-O(1W)
Na(1)-N(6)#2
Na(2)-N(4)
Na(2)-O(3W)
Na(2)-O(21)
B(1)-O(3)
B(1)-O(19)
B(1)-O(4)
B(1)-O(14)
C(1)-N(3)
O(1W)-Na(1)-O(16)#1
N(5)-Na(1)-O(1W)
N(4)- Na(2)-O(3W)
O(3)-B(1)-O(19) / 1.909(14)
2.42(5)
1.678(12)
1.830(15)
1.902(15)
2.45(2)
1.86(2)
1.653(13)
1.856(13)
1.856(15)
1.892(14)
2.41(2)
2.43(2)
1.83(2)
2.18(3)
2.66(3)
1.94(2)
2.007(10)
2.63(2)
1.49(5)
1.52(2)
1.53(2)
1.61(2)
1.44(2)
132.1 (9)
115.8(12)
79(9)
67(2)
Symmetry transformations used to generate equivalent atoms: #1 -x+3/2,-y+1/2,-z+1;
#2 x+1/2,y+1/2,z; #3 x-1/2,y+1/2,z; #4 x+1/2,y-1/2,z #5 x-1/2,y-1/2,z.
Fig S1. TG curve obtained from compound 1.
Fig S2. The experimental (red line) and simulated (black line) PXRD patterns obtained from compounds 1.
Proposed mechanisms for electrocatalytic reduction of nitrite by compound 1:
BWVI12-nWVnO40(4+n)- + NO2- + xH+ → BWVI12O404- + products (containing N) (1)
BWVI12-nWVnO40(4+n)- + NO + yH+ → BWVI12O404- + products (containing N) (2)
Table S2. CAT% data of compound1 toward reduction of nitrite.
CAT%substrate / Compound 1
Nitrite / 2 ´ 10-3M / 20
4 ´ 10-3 M / 80
6 ´ 10-3 M / 280
8 ´ 10-3 M / 550
Proposed reason for change of Na-O/N bond lengths in compound 1:
The Na-O distances are in the range from 2.007 Å to 2.63 Å, and the Na-N distances are in the range from 1.83 Å to 2.66 Å. which are shorter than Na-O/N bond lengths in other reported Na compounds [1-2]. We deduce that there is weak interaction between Na-complex and POMs by using theoretical calculation. All the DFT calculations were carried out using Gaussian 09 software package. Color-filled reduced density gradient isosurface for the weak interaction and color-filled map of localized orbital locator were performed by the Multifunctional Wave function Analyzer (Multiwfn) software at the B3LYP/6-31G(d) level [3-7], the corresponding graphs were also output using Visual Molecular Dynamics (VMD). The bond lengths of Na-N in Na-tib complexes without POMs are 2.332 Å (Fig 1a), the range of Na-N bond distance in compound 1 is 1.829-1.936 Å (Fig 1b). The results show that introducing POMs change Na-N bond lengths in the structure of compound 1.
Figure. 1 The structural parameters of Na-tib complex and compound 1. (Colorcode:Na,violet; W, mazarine; N, sky blue; C,gray)
Fig 2 shows the color-filled reduced density gradient (RDG) isosurface of compound 1，recall the color scale bar, blue, green and red regions represent strong attraction(H-bond, Halogen-bond), Van der Waals and strong repulsion (Steric effect in ring or cage), respectively. From the color-filled RDG isosurface of the title compound, Van der Waals interaction is a crucial factor to influence the change of Na-O/N bond distance, make Na-O/N bond shorter in compound 1.
Figure. 2 Color-filled reduced density gradient isosurface for the weak interaction of the title compound. (color bar: Theblue, greenand red regionsrepresentstrong attraction, Van der Waals interaction and strong repulsion, respectively)
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