Citation: LIU Chun-Guang, ZHANG Han-Yu, JIANG Meng-Xu. DFT Study of Mono-Manganese-Substituted Keggin-Type Polyoxometalates with Atmospheric Small Molecules X (X=H₂O, N₂, O₂, NO, N₂O, CO and CO₂)[J]. Chinese Journal of Inorganic Chemistry, ;2018, 34(6): 1127-1136. doi: 10.11862/CJIC.2018.143 shu

DFT Study of Mono-Manganese-Substituted Keggin-Type Polyoxometalates with Atmospheric Small Molecules X (X=H₂O, N₂, O₂, NO, N₂O, CO and CO₂)

College of Chemical Engineering, Northeast Electric Power University, Jilin, Jilin 132012, China

Corresponding author: LIU Chun-Guang, liucg407@163.com
Received Date: 24 October 2017
Revised Date: 13 February 2018

Figures(2)

Geometries, electronic structure, and bonding nature of a series of mono-manganese-substituted Keggin-type (POMs) with atmospheric small molecules X (X=H₂O, N₂, O₂, NO, N₂O, CO and CO₂) have been studied based on density functional theory (DFT) method with M06L functional. Due to the poly-anionic nature of polyoxometalates (POMs), the counterions effects have firstly been considered by means of a full treatment of the cesium salt Cs₄[PW₁₁O₃₉Mn^ⅢH₂O]. DFT-M06L calculations show that the key geometric a nd electronic parameters are almost constants as change of the four Cs counterions. The optimized calculations for[PW₁₁O₃₉Mn^ⅢH₂O]^4-both in gas phase and solution provide an analogous result, no significant variation of key geometric and electronic parameters was found when compared with the cesium salt. The calculated relative energy of different spin states indicates that the lowest energy spin state is the high-spin quintet state for[PW₁₁O₃₉Mn^ⅢX]^4-(X=H₂O, N₂, N₂O, CO and CO₂), triplet state for[PW₁₁O₃₉Mn^ⅢO₂]^4-, and doublet state for[PW₁₁O₃₉Mn^ⅢNO]^4-. The calculated adsorption energy of those atmospheric small molecules over the porphyrin-like POM ligand increases in the following order:N₂ < N₂O < CO≈CO₂ < O₂ < H₂O < NO. The Mn-NO POM complex provides considerable adsorption energy. Mulliken population analysis shows that coordination of NO ligand to the Mn^Ⅲ center in its doublet ground state arises from an antiferromagnetic coupling between an intermediate-spin Mn^Ⅲ center and NO^· unit.
- density functional theory,
- electronic configuration,
- polyoxometalates,
- atmospheric small molecules
1. [1]
  Kozhevnikov I V. Chem. Rev., 1998, 98:171-198 doi: 10.1021/cr960400y
2. [2]
  Weinstock I A. Chem. Rev., 1998, 98:113-170 doi: 10.1021/cr9703414
3. [3]
  Mizuno N, Misono M. Chem. Rev., 1998, 98:199-218 doi: 10.1021/cr960401q
4. [4]
  Dolbecq A, Dumas E, Mayer C R, et al. Chem. Rev., 2010, 110:6009-6048 doi: 10.1021/cr1000578
5. [5]
  Sun M, Zhang J, Putaj P, et al. Chem. Rev., 2014, 114:981-1019 doi: 10.1021/cr300302b
6. [6]
  Wang S S, Yang G Y. Chem. Rev., 2015, 115:4893-4963 doi: 10.1021/cr500390v
7. [7]
  Vilà-Nadal L, Mitchell S G, Rodríguez-Fortea A, et al. Phys. Chem. Chem. Phys., 2011, 13:20136-20145 doi: 10.1039/c1cp21209e
8. [8]
  Vilà-Nadal L, Mitchell S G, Long D L, et al. Dalton Trans., 2012, 41:2264-2271 doi: 10.1039/C2DT11919F
9. [9]
  McGlone T, Vilà-Nadal L, Miras H N, et al. Dalton Trans., 2010, 39:11599-11604 doi: 10.1039/c0dt01327g
10. [10]
  Rubinstein A, Jiménez-Lozanao P, Carbó J J, et al. J. Am. Chem. Soc., 2014, 136:10941-10948 doi: 10.1021/ja502846h
11. [11]
  Marrot J, Pilette M A, Haouas M, et al. J. Am. Chem. Soc., 2012, 134:1724-1737 doi: 10.1021/ja2090383
12. [12]
  FAN Ying, LIU Shi-Zhong. Chinese J. Inorg. Chem., 2002, 18:635-638 doi: 10.3321/j.issn:1001-4861.2002.06.020
13. [13]
  Khenkin A M, Kumar D, Shaik S, et al. J. Am. Chem. Soc., 2006, 128:15451-15460 doi: 10.1021/ja0638455
14. [14]
  Liu C G, Liu S, Zheng T. Inorg. Chem., 2015, 54:7929-7935 doi: 10.1021/acs.inorgchem.5b01002
15. [15]
  Liu C G, Su Z M, Guan W. Inorg. Chem., 2009, 48:541-548 doi: 10.1021/ic8012443
16. [16]
  Liu C G, Guan W, Yan L K, et al. Dalton Trans., 2011, 40:2967-2974 doi: 10.1039/c0dt01085e
17. [17]
  Liu C G, Guan W, Yan L K, et al. Dalton Trans., 2009, 38:6208-6213
18. [18]
  Poblet J M, López X, Bo C, et al. Chem. Soc. Rev., 2003, 32:297-308 doi: 10.1039/B109928K
19. [19]
  López X, Carbó J J, Bo C, et al. Chem. Soc. Rev., 2012, 41:7537-7571 doi: 10.1039/c2cs35168d
20. [20]
  Maestre J M, López X, Bo C, et al. J. Am. Chem. Soc., 2001, 123:3749-3758 doi: 10.1021/ja003563j
21. [21]
  Antonova N S, Carbó J J, Kortz U, et al. J. Am. Chem. Soc., 2010, 132:7488-7497 doi: 10.1021/ja1023157
22. [22]
  Efremenko I, Neumann R. J. Am. Chem. Soc., 2012, 134:20669-20680 doi: 10.1021/ja308625q
23. [23]
  Hill C L, Brown R B. J. Am. Chem. Soc., 1986, 108:536-538 doi: 10.1021/ja00263a046
24. [24]
  Mansuy D, Bartoli J F, Battioni P, et al. J. Am. Chem. Soc., 1991, 113:7222-7226 doi: 10.1021/ja00019a019
25. [25]
  Karpuschkin T, Kappes M M, Hampe O. Angew. Chem. Int. Ed., 2013, 52:10374-10377 doi: 10.1002/anie.201303200
26. [26]
  Chen O, Groh S, Liechty A, et al. J. Am. Chem. Soc., 1999, 121:11910-11911 doi: 10.1021/ja991477h
27. [27]
  Kano K, Itoh Y, Kitagishi H, et al. J. Am. Chem. Soc., 2008, 130:8006-8015 doi: 10.1021/ja8009583
28. [28]
  Wasser I M, Huang H W, Moenne-Loccoz P, et al. J. Am. Chem. Soc., 2005, 127:3310-3320 doi: 10.1021/ja0458773
29. [29]
  Morris A J, Meyer G J, Fujita E. Acc. Chem. Res., 2009, 42:1983-1994 doi: 10.1021/ar9001679
30. [30]
  Groves J T, Roman J S. J. Am. Chem. Soc., 1995, 117:5594-5595 doi: 10.1021/ja00125a025
31. [31]
  Saito S, Ohtake H, Umezawa N, et al. Chem. Commun., 2013, 49:8979-8981 doi: 10.1039/c3cc43912g
32. [32]
  Phougat N, Vasudevan P, Jha N K, et al. Transition Metal Chem., 2003, 28:838-847 doi: 10.1023/A:1026095426207
33. [33]
  Meunier B. Chem. Rev., 1992, 92:1411-1456 doi: 10.1021/cr00014a008
34. [34]
  Liu L, Yu M, Wayland B B, et al. Chem. Commun., 2010, 46:6353-6355 doi: 10.1039/c0cc01406k
35. [35]
  Abdurahman A, Renger T. J. Phys. Chem. A, 2009, 113:9202-9206 doi: 10.1021/jp9032657
36. [36]
  Zhao Y, Truhlar D G. J. Chem. Phys., 2006, 125:1-18
37. [37]
  Hay P J, Wadt W R. J. Chem. Phys., 1985, 82:270-283 doi: 10.1063/1.448799
38. [38]
  Wadt W R, Hay P J. J. Chem. Phys., 1985, 82:284-293 doi: 10.1063/1.448800
39. [39]
  Hay P J, Wadt W R. J. Chem. Phys., 1985, 82:299-310 doi: 10.1063/1.448975
40. [40]
  Tomasi J, Mennucci B, Cammi R. Chem. Rev., 2005, 105:2999-3093 doi: 10.1021/cr9904009
41. [41]
  Frisch M J, Trucks G W, Schlegel H B, et al. Gaussian, Inc., Wallingford CT, 2009, Gaussian 09, Revision D. 01
42. [42]
  Kirby J F, Baker L C W. Inorg. Chem., 1998, 37:5537-5543 doi: 10.1021/ic971382l
43. [43]
  Brevard C, Schimpf R, Tourne G, et al. J. Am. Chem. Soc., 1983, 105:7059-7063 doi: 10.1021/ja00362a008
44. [44]
  Grigoriev V A, Cheng D, Hill C L, et al. J. Am. Chem. Soc., 2001, 123:52925307
45. [45]
  Kato C N, Kashiwagi T, Unno W, et al. Inorg. Chem., 2014, 53:4824-4832 doi: 10.1021/ic402650g
46. [46]
  Mizuno N, Min J S, Taguchi A. Chem. Mater., 2004, 16:2809-2825
47. [47]
  Bi L H, Reicke M, Kortz U, et al. Inorg. Chem., 2004, 43:3915-3920 doi: 10.1021/ic049736d
48. [48]
  Pamplin C B, Ma E S F, Safari N, et al. J. Am. Chem. Soc., 2001, 123:8596-8597 doi: 10.1021/ja0106319
49. [49]
  Groves J T, Roman J S. J. Am. Chem. Soc., 1995, 117:5594-5595 doi: 10.1021/ja00125a025
50. [50]
  Groves J T, Quinn R. J. Am. Chem. Soc., 1985, 107:5790-5791 doi: 10.1021/ja00306a029
51. [51]
  Ben-Daniel R, Weiner L, Neumann R. J. Am. Chem. Soc., 2002, 124:8788-8789 doi: 10.1021/ja0259077
52. [52]
  Ghosh A. Acc. Chem. Res., 2005, 38:943-954 doi: 10.1021/ar050121+
53. [53]
  Kachalova G S, Pepov A N, Bartunik H D. Science, 1999, 284:473-476 doi: 10.1126/science.284.5413.473
54. [54]
  Spiro T G, Kozlowski P M. J. Am. Chem. Soc., 1998, 120:4524-4525 doi: 10.1021/ja9732946
55. [55]
  Rovira C, Kunc K, Hutter J, et al. Int. J. Quantum Chem., 1998, 69:31-35 doi: 10.1002/(ISSN)1097-461X
1. [1]
  Maitri Bhattacharjee , Rekha Boruah Smriti , R. N. Dutta Purkayastha , Waldemar Maniukiewicz , Shubhamoy Chowdhury , Debasish Maiti , Tamanna Akhtar . Synthesis, structural characterization, bio-activity, and density functional theory calculation on Cu(Ⅱ) complexes with hydrazone-based Schiff base ligands. Chinese Journal of Inorganic Chemistry, 2024, 40(7): 1409-1422. doi: 10.11862/CJIC.20240007
2. [2]
  Jie ZHAO , Sen LIU , Qikang YIN , Xiaoqing LU , Zhaojie WANG . Theoretical calculation of selective adsorption and separation of CO₂ by alkali metal modified naphthalene/naphthalenediyne. Chinese Journal of Inorganic Chemistry, 2024, 40(3): 515-522. doi: 10.11862/CJIC.20230385
3. [3]
  Huipeng Zhao , Xiaoqiang Du . Polyoxometalates as the redox anolyte for efficient conversion of biomass to formic acid. Chinese Journal of Structural Chemistry, 2024, 43(2): 100246-100246. doi: 10.1016/j.cjsc.2024.100246
4. [4]
  Aolei Tan , Xiaoxiao Ma . Exploring the functional roles of small-molecule metabolites in disease research: Recent advancements in metabolomics. Chinese Chemical Letters, 2024, 35(8): 109276-. doi: 10.1016/j.cclet.2023.109276
5. [5]
  Shuyan ZHAO . Field-induced Co^Ⅱ single-ion magnet with pentagonal bipyramidal configuration. Chinese Journal of Inorganic Chemistry, 2024, 40(8): 1583-1591. doi: 10.11862/CJIC.20240231
6. [6]
  Zhenyang Lin . A classification scheme for inorganic cluster compounds based on their electronic structures and bonding characteristics. Chinese Journal of Structural Chemistry, 2024, 43(5): 100254-100254. doi: 10.1016/j.cjsc.2024.100254
7. [7]
  Zhigang Zeng , Changzhou Liao , Lei Yu . Molecules for COVID-19 treatment. Chinese Chemical Letters, 2024, 35(7): 109349-. doi: 10.1016/j.cclet.2023.109349
8. [8]
  Hanqing Zhang , Xiaoxia Wang , Chen Chen , Xianfeng Yang , Chungli Dong , Yucheng Huang , Xiaoliang Zhao , Dongjiang Yang . Selective CO2-to-formic acid electrochemical conversion by modulating electronic environment of copper phthalocyanine with defective graphene. Chinese Journal of Structural Chemistry, 2023, 42(10): 100089-100089. doi: 10.1016/j.cjsc.2023.100089
9. [9]
  Jianmei Han , Peng Wang , Hua Zhang , Ning Song , Xuguang An , Baojuan Xi , Shenglin Xiong . Performance optimization of chalcogenide catalytic materials in lithium-sulfur batteries: Structural and electronic engineering. Chinese Chemical Letters, 2024, 35(7): 109543-. doi: 10.1016/j.cclet.2024.109543
10. [10]
  Shiqi Peng , Yongfang Rao , Tan Li , Yufei Zhang , Jun-ji Cao , Shuncheng Lee , Yu Huang . Regulating the electronic structure of Ir single atoms by ZrO₂ nanoparticles for enhanced catalytic oxidation of formaldehyde at room temperature. Chinese Chemical Letters, 2024, 35(7): 109219-. doi: 10.1016/j.cclet.2023.109219
11. [11]
  Kun Zhang , Ni Dan , Dan-Dan Ren , Ruo-Yu Zhang , Xiaoyan Lu , Ya-Pan Wu , Li-Lei Zhang , Hong-Ru Fu , Dong-Sheng Li . A small D-A molecule with highly heat-resisting room temperature phosphorescence for white emission and anti-counterfeiting. Chinese Journal of Structural Chemistry, 2024, 43(3): 100244-100244. doi: 10.1016/j.cjsc.2024.100244
12. [12]
  Xianxu Chu , Lu Wang , Junru Li , Hui Xu . Surface chemical microenvironment engineering of catalysts by organic molecules for boosting electrocatalytic reaction. Chinese Chemical Letters, 2024, 35(8): 109105-. doi: 10.1016/j.cclet.2023.109105
13. [13]
  Yunfei Shen , Long Chen . Gradient imprinted Zn metal anodes assist dendrites-free at high current density/capacity. Chinese Journal of Structural Chemistry, 2024, 43(10): 100321-100321. doi: 10.1016/j.cjsc.2024.100321
14. [14]
  Uttam Pandurang Patil . Porous carbon catalysis in sustainable synthesis of functional heterocycles: An overview. Chinese Chemical Letters, 2024, 35(8): 109472-. doi: 10.1016/j.cclet.2023.109472
15. [15]
  Qihan Lin , Jiabin Xing , Yue-Yang Liu , Gang Wu , Shi-Jia Liu , Hui Wang , Wei Zhou , Zhan-Ting Li , Dan-Wei Zhang . taBOX: A water-soluble tetraanionic rectangular molecular container for conjugated molecules and taste masking for berberine and palmatine. Chinese Chemical Letters, 2024, 35(5): 109119-. doi: 10.1016/j.cclet.2023.109119
16. [16]
  Jie Zhou , Quanyu Li , Xiaomeng Hu , Weifeng Wei , Xiaobo Ji , Guichao Kuang , Liangjun Zhou , Libao Chen , Yuejiao Chen . Water molecules regulation for reversible Zn anode in aqueous zinc ion battery: Mini-review. Chinese Chemical Letters, 2024, 35(8): 109143-. doi: 10.1016/j.cclet.2023.109143
17. [17]
  Zhao-Xia Lian , Xue-Zhi Wang , Chuang-Wei Zhou , Jiayu Li , Ming-De Li , Xiao-Ping Zhou , Dan Li . Producing circularly polarized luminescence by radiative energy transfer from achiral metal-organic cage to chiral organic molecules. Chinese Chemical Letters, 2024, 35(8): 109063-. doi: 10.1016/j.cclet.2023.109063
18. [18]
  Renshu Huang , Jinli Chen , Xingfa Chen , Tianqi Yu , Huyi Yu , Kaien Li , Bin Li , Shibin Yin . Synergized oxygen vacancies with Mn2O3@CeO2 heterojunction as high current density catalysts for Li–O2 batteries. Chinese Journal of Structural Chemistry, 2023, 42(11): 100171-100171. doi: 10.1016/j.cjsc.2023.100171
19. [19]
  Shuanglin TIAN , Tinghong GAO , Yutao LIU , Qian CHEN , Quan XIE , Qingquan XIAO , Yongchao LIANG . First-principles study of adsorption of Cl₂ and CO gas molecules by transition metal-doped g-GaN. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1189-1200. doi: 10.11862/CJIC.20230482
20. [20]
  Huyi Yu , Renshu Huang , Qian Liu , Xingfa Chen , Tianqi Yu , Haiquan Wang , Xincheng Liang , Shibin Yin . Te-doped Fe3O4 flower enabling low overpotential cycling of Li-CO2 batteries at high current density. Chinese Journal of Structural Chemistry, 2024, 43(3): 100253-100253. doi: 10.1016/j.cjsc.2024.100253

Get Citation

PDF

XML

Metrics

PDF Downloads(4)
Abstract views(291)
HTML views(44)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

DFT Study of Mono-Manganese-Substituted Keggin-Type Polyoxometalates with Atmospheric Small Molecules X (X=H2O, N2, O2, NO, N2O, CO and CO2)

Metrics

通讯作者: 陈斌, bchen63@163.com

DFT Study of Mono-Manganese-Substituted Keggin-Type Polyoxometalates with Atmospheric Small Molecules X (X=H₂O, N₂, O₂, NO, N₂O, CO and CO₂)