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Three-propeller-blade-shaped electride: remarkable alkali-metal-doped effect on the first hyperpolarizability

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Abstract

Significant alkali-metal-doped effects on the structure and the first hyperpolarizability (β 0) of effective multi-nitrogen complexant tris[(2-imidazolyl)methyl]amine (TIMA) are investigated. Three imidazoles of TIMA like three blades of propeller connect with methyls by the C–C single bonds. Because of the three C–C single-bond cooperative rotations, the TIMA behaves with great flexibility, and it is a high-performance multi-nitrogen complexant for the alkali metal doping. Thus, the new complexes Am-TIMA (Am = Li, Na, and K) with electride characteristic have diffuse excess electron than the reported electride-type system due to the strong interaction between the complexant TIMA and alkali metal. For the first hyperpolarizability, three engaging electrides Am-TIMA with the diffuse excess electrons exhibit considerably large β 0 values using the MP2 (full) method and the β 0 values of new electrides are greatly larger (3,464–29,705 times) than that (338 au) of TIMA. Surprisingly, the K-TIMA sets a new record β 0 value to be 1.00 × 107 au which far exceeds than that (3,694–76,978 au) of the reported electride-type system Li@calix[4]pyrrole (J Am Chem Soc 127:10977–10981, 2005) and Lin−H−(CF2−CH2)3−H (n = 1, 2) (J Am Chem Soc 129:2967–2970, 2007) and 31,123 au of the organometallic system (J Am Chem Soc 121:4047–4053, 1999) Ru(trans-4,4′-diethylaminostyryl-2,2′-bipyridine) 2+3 , as well as 1.23 × 106 au of the large donor-CNT systems (Nano Lett 8:2814–2818, 2008). Clearly, the alkali-metal-doped effect on the first hyperpolarizability is very dramatic for the high-performance multi-nitrogen complexant TIMA. Considering simple possibility from molecule to material, the β 0 values of optimized Li-TIMA-dimer and Li-TIMA-tetramer are investigated by BHandHLYP method. Interestingly, results show that the order of β 0 value is Li-TIMA-monomer < Li-TIMA-dimer < Li-TIMA-tetramer. So the new three-propeller-blade-shaped electrides can be considered as candidates for high-performance nonlinear optical materials.

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Acknowledgments

This work was supported by the National Natural Science Foundation of China (No. 20773046, 20703008, and 21003019), and Chang Jiang Scholars Program (2006), Program for Changjiang Scholars and Innovative Research Team in University (IRT0714), Science Foundation of Young Teachers of Northeast Normal University (20090402 and 09QNJJ008) and project supported by the Foundation for Young Scholars of Jilin Province, China (Grant No. 20100178 and 20100114).

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  1. Faculty of Chemistry, Institute of Functional Material Chemistry, Northeast Normal University, 130024, Changchun, Jilin, People’s Republic of China

    Hong-Liang Xu, Shi-Ling Sun, Shabbir Muhammad & Zhong-Min Su

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  1. Hong-Liang Xu
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  2. Shi-Ling Sun
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  3. Shabbir Muhammad
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  4. Zhong-Min Su
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Correspondence to Zhong-Min Su.

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Xu, HL., Sun, SL., Muhammad, S. et al. Three-propeller-blade-shaped electride: remarkable alkali-metal-doped effect on the first hyperpolarizability. Theor Chem Acc 128, 241–248 (2011). https://doi.org/10.1007/s00214-010-0837-0

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