Adaptability of Electron-Localization Strategy for Achieving Planar Tetracoordination: Nitrogen versus Carbon

Xiu-dong Jia^{1, 2},
Jian-hong Bian^{1, 2, 3},
Bo Jin^{1, 2},
Rui Sun^{1, 2},
Bin Huo^{1, 2},
Xiao-ling Guan^{1, 2},
Chen-fei Guo^{1, 2},
Caixia Yuan^{1, 2
, ,},
Yan-bo Wu^{1, 2
, ,}

1.
Key Laboratory of Materials for Energy Conversion and Storage of Shanxi Province, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China
2.
Key Laboratory of Chemical Biology and Molecular Engineering of Ministry of Education, Institute of Molecular Science, Shanxi University, Taiyuan 030006, China
3.
Department of Materials and Chemical Engineering, Taiyuan University, Taiyuan 030032, China

More Information

Corresponding author: Email: cxyuan@sxu.edu.cn; wyb@sxu.edu.cn

摘要

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Abstract: A case study has been performed on the adaptability of electron-localization strategy in designing clusters with planar tetracoordinate nitrogen (ptN) through the detailed comparison between ptN clusters NLi₃E⁺ (E = N, P, As) and their ptC counterparts CLi₃E (E = N, P, As). The results revealed that NLi₃E⁺ clusters possessed similar planar geometries to CLi₃E, which are both determined by the existence of a localized π bond. Nevertheless, NLi₃E⁺ clusters possess the obviously higher electronic, thermodynamic, and dynamic stabilities than CLi₃E clusters, as reflected by wider HOMO–LUMO gaps (4.58–4.68 eV versus 2.10–2.74 eV), the overall lower-lying positions on potential energy surfaces verified at the CCSD(T)/aug-cc-pVTZ level, and better rigidity during the molecular dynamic simulations at the PBE/DZVP level. Therefore, our results suggest that electron-localization strategy may be more suitable for designing the clusters, whose central atom possesses relatively higher electronegativity and more favours the localized bond. In addition, due to the good stability, the cationic NLi₃E⁺ clusters designed in this work are suitable for gas phase generation, mass-selection, and spectroscopic characterization.
- Electron-localization /
- Electron-delocalization /
- Planar tetracoordinate nitrogen /
- Potential energy surface /
- Molecular dynamic simulation /
- Stability

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Figure 1. CCSD(T)/aug-cc-pVTZ-optimized structures of NLi₃E⁺ (E = N, P, As) (1a–3a) with necessary bond lengths (in Å) regarding symmetry. The Wiberg bond orders calculated at the B3LYP/aug-cc-pVTZ level for N–E interactions are given in italic red font.

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Figure 2. Valence canonical molecular orbitals (A) and AdNDP bonding patterns (B) with occupation numbers (ONs) of N₂Li₃⁺ (1a).

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Figure 3. Comparison of HOMO–LUMO gaps (Gap) between NLi₃E⁺ [E = N (1a), P (2a), As (3s)] and CLi₃E [E = N (1a'), P (2a'), As (3a')] species at the B2PLYP-D3(BJ)/aug-cc-pVTZ level.

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Figure 4. Structures and relative energies (∆E, in kcal/mol) of 1a–3a and their low-energy isomers at the CCSD(T)/aug-cc-pVTZ level.

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Figure 5. RMSD plots for the BOMD simulations of NLi₃E⁺ and CLi₃E (E = N, P, As) (1a–3a and 1a′–3a′) at 4, 298 and 500 K.

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参考文献(42)

[1]	R. Hoffmann, R. W. Alder, and C. F. Wilcox, J. Am. Chem. Soc. 92, 4992 (1970). doi: 10.1021/ja00719a044
[2]	J. H. van’t Hoff, Arch. Neerl. Sci. Exactes Nat. 9, 445 (1874).
[3]	J. A. Le Bel, Bull. Soc. Chim. Fr. 22, 337 (1874).
[4]	R. Hoffmann, Pure. Appl. Chem. 28, 181 (1971). doi: 10.1351/pac197128020181
[5]	K. Sorger and P. v. R. Schleyer, J. Mol. Struc.: THEOCHEM 338, 317 (1995). doi: 10.1016/0166-1280(95)04233-V
[6]	L. Radom and D. R. Rasmussen, Pure Appl. Chem. 70, 1977 (1998). doi: 10.1351/pac199870101977
[7]	D. Rottger and G. Erker, Angew. Chem. Int. Ed. Engl. 36, 812 (1997). doi: 10.1002/anie.199708121
[8]	W. Siebert and A. Gunale, Chem. Soc. Rev. 28, 367 (1999). doi: 10.1039/a801225c
[9]	R. Choukroun and P. Cassoux, Acc. Chem. Res. 32, 494 (1999). doi: 10.1021/ar970304z
[10]	L. S. Wang, A. I. Boldyrev, X. Li, and J. Simons, J. Am. Chem. Soc. 122, 7681 (2000). doi: 10.1021/ja993081b
[11]	J. B. Collins, J. D. Dill, E. D. Jemmis, Y. Apeloig, P. v. R. Schleyer, R. Seeger, and J. A. Pople, J. Am. Chem. Soc. 98, 5419 (1976). doi: 10.1021/ja00434a001
[12]	L. M. Yang, E. Ganz, Z. Chen, Z. X. Wang, and P. v. R. Schleyer, Angew. Chem. Int. Ed. 54, 9468 (2015). doi: 10.1002/anie.201410407
[13]	V. Vassilev-Galindo, S. Pan, K. J. Donald, and G. Merino, Nat. Rev. Chem. 2, 0114 (2018). doi: 10.1038/s41570-018-0114
[14]	P. Liu, J. H. Bian, Q. Wang, F. Huang, D. Li, and Y. B. Wu, Phys. Chem. Chem. Phys. 20, 12642 (2018). doi: 10.1039/C8CP01193A
[15]	X. F. Zhao, J. H. Bian, F. Huang, C. Yuan, Q. Wang, P. Liu, D. Li, X. Wang, and Y. B. Wu, RSC Adv. 8, 36521 (2018). doi: 10.1039/C8RA07664B
[16]	S. Pan, J. L. Cabellos, M. Orozco-Ic, P. K. Chattaraj, L. Zhao, and G. Merino, Phys. Chem. Chem. Phys. 20, 12350 (2018). doi: 10.1039/C8CP01009A
[17]	J. C. Guo, L. Y. Feng, C. Dong, and H. J. Zhai, J. Phys. Chem. A 122, 8370 (2018). doi: 10.1021/acs.jpca.8b08573
[18]	J. C. Guo, L. Y. Feng, J. Barroso, G. Merino, and H. J. Zhai, Chem. Commun. 56, 8305 (2020). doi: 10.1039/D0CC02973D
[19]	M. H. Wang, X. Dong, Y. H. Ding, and Z. H. Cui, Chem. Commun. 56, 7285 (2020). doi: 10.1039/D0CC02236E
[20]	R. Sun, X. F. Zhao, B. Jin, B. Huo, J. H. Bian, X. L. Guan, C. Yuan, and Y. B. Wu, Phys. Chem. Chem. Phys. 22, 17062 (2020). doi: 10.1039/D0CP01106A
[21]	J. H. Bian, B. Jin, X. F. Zhao, R. Sun, C. Yuan, C. Y. Zhou, and Y. B. Wu, RSC Adv. 11, 15841 (2021). doi: 10.1039/D1RA02178H
[22]	B. Jin, R. Sun, B. Huo, C. Yuan, and Y. B. Wu, Chem. Commun. 57, 13716 (2021). doi: 10.1039/D1CC05844D
[23]	R. Sun, B. Jin, B. Huo, C. Yuan, H. J. Zhai, and Y. B. Wu, Chem. Commun. 58, 2552 (2022). doi: 10.1039/D1CC07313C
[24]	B. Jin and Z. R. Wang, Phys. Chem. Chem. Phys. 24, 17956 (2022). doi: 10.1039/D2CP01496C
[25]	Z. H. Cui, C. B. Shao, S. M. Gao, and Y H. Ding, Phys. Chem. Chem. Phys. 12, 13637 (2010). doi: 10.1039/c0cp00296h
[26]	Z. H. Cui, Y. H. Ding, J. L. Cabellos, E. Osorio, R. Islas, A. Restrepo, and G. Merino, Phys. Chem. Chem. Phys. 17, 8769 (2015). doi: 10.1039/C4CP05707D
[27]	J. Y. Guo, H. Y. Chai, Q. Duan, J. M. Qin, X. D. Shen, D. Y. Jiang, J. H. Hou, B. Yan, Z. R. Li, F. L. Gu, and Q. S. Li, Phys. Chem. Chem. Phys. 18, 4589 (2016). doi: 10.1039/C5CP06081H
[28]	Y. B. Wu, H. G. Lu, S. D. Li, and Z. X. Wang, J. Phys. Chem. A 113, 3395 (2009). doi: 10.1021/jp8099187
[29]	Y. B. Wu, Z. X. Li, X. H. Pu, and Z. X. Wang, J. Phys. Chem. C 115, 13187 (2011). doi: 10.1021/jp202200p
[30]	Y. B. Wu, Z. X. Li, X. H. Pu, and Z. X. Wang, Comput. Theor. Chem. 992, 78 (2012). doi: 10.1016/j.comptc.2012.05.008
[31]	M. H. Wang, M. Orozco-Ic, L. Leyva-Parra, W. Tiznado, J. Barroso, Y. H. Ding, Z. H. Cui, and G. Merino, J. Phys. Chem. A 125, 3009 (2021). doi: 10.1021/acs.jpca.1c02002
[32]	Z. H. Cui and Y. H. Ding, Phys. Chem. Chem. Phys. 13, 5960 (2011). doi: 10.1039/c0cp02475a
[33]	A. E. Reed, L. A. Curtiss, and F. Weinhold, Chem. Rev. 88, 899 (1988). doi: 10.1021/cr00088a005
[34]	D. Y. Zubarev and A. I. Boldyrev, Phys. Chem. Chem. Phys. 10, 5207 (2008). doi: 10.1039/b804083d
[35]	M. Saunders, J. Comput. Chem. 25, 621 (2004). doi: 10.1002/jcc.10407
[36]	P. P. Bera, K. W. Sattelmeyer, M. Saunders, H. F. Schaefer, and P. v. R. Schleyer, J. Phys. Chem. A 110, 4287 (2006). doi: 10.1021/jp057107z
[37]	T. D. Kühne, M. Iannuzzi, M. Del Ben, M. V. V. Rybkin, P. Seewald, F. Stein, T. Laino, R. Z. Khaliullin, O. Schütt, F. Schiffmann, D. Golze, J. Wilhelm, S. Chulkov, M. H. Bani-Hashemian, V. Weber, U. Borštnik, M. Taillefumier, A. S. Jakobovits, A. Lazzaro, H. Pabst, T. Müller, R. Schade, M. Guidon, S. Andermatt, N. Holmberg, G. K. Schenter, A. Hehn, A. Bussy, F. Belleflamme, G. Tabacchi, A. Glöß, M. Lass, I. Bethune, C. J. Mundy, C. Plessl, M. Watkins, J. VandeVondele, M. Krack, and J. Hutter, J. Chem. Phys. 152, 194103 (2020). doi: 10.1063/5.0007045
[38]	H. G. Lu and Y. B. Wu, in GXYZ 2.0, A Random Search Program, Taiyuan: Shanxi University, (2015).
[39]	The AdNDP program was downloaded freely at http:// ion.chem.usu.edu/~boldyrev/adndp.php.
[40]	H. J. Werner, P. J. Knowles, G. Knizia, F. R. Manby, M. Schütz, P. Celani, T. Korona, R. Lindh, A. Mitrushenkov, G. Rauhut, K. R. Shamasundar, T. B. Adler, R. D. Amos, A. Bernhardsson, A. Berning, D. L. Cooper, M. J. O. Deegan, A. J. Dobbyn, F. Eckert, E. Goll, C. Hampel, A. Hesselmann, G. Hetzer, T. Hrenar, G. Jansen, C. Köppl, Y. Liu, A. W. Lloyd, R. A. Mata, A. J. May, S. J. Mcnicholas, W. Meyer, M. E. Mura, A. Nicklass, D. P. O’Neill, P. Palmieri, D. Peng, K. Pflüger, R. Pitzer, M. Reiher, T. Shiozaki, H. Stoll, A. J. Stone, R. Tarroni, T. Thorsteinsson, and M. Wang, MolPro, a package of ab initio programs, version 2012.1, (2012).
[41]	M. J. Frisch, G. W. Trucks, H. B. Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, G. Scalmani, V. Barone, G. A. Petersson, H. Nakatsuji, X. Li, M. Caricato, A. V. Marenich, J. Bloino, B. G. Janesko, R. Gomperts, B. Mennucci, H. P. Hratchian, J. V. Ortiz, A. F. Izmaylov, J. L. Sonnenberg, D. Williams-Young, F. Ding, F. Lipparini, F. Egidi, J. Goings, B. Peng, A. Petrone, T. Henderson, D. Ranasinghe, V. G. Zakrzewski, J. Gao, N. Rega, G. Zheng, W. Liang, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J. Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, K. Throssell, J. A. Jr, J. E. P. Montgomery, F. Ogliaro, M. J. Bearpark, J. J. Heyd, E. N. Brothers, K. N. Kudin, V. N. Staroverov, T. A. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A. P. Rendell, J. C. Burant, S. S. Iyengar, J. Tomasi, M. Cossi, J. M. Millam, M. Klene, C. Adamo, R. Cammi, J. W. Ochterski, R. L. Martin, K. Morokuma, O. Farkas, J. B. Foresman, and D. J. Fox, Gaussian 16, vision B. 01, Wallingford CT: Gaussian Inc., (2016).
[42]	P. Pyykkö, J. Phys. Chem. A 119, 2326 (2015). doi: 10.1021/jp5065819