Quantum Mechanical Design and Structure of the Li@B 10 H 14 Basket with a Remarkably Enhanced Electro-Optical Response Shabbir Muhammad, Hongliang Xu, Yi Liao, Yuhe Kan, and Zhongmin Su* Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal UniVersity, Changchun 130024, People’s Republic of China Received April 22, 2009; E-mail: zmsu@nenu.edu.cn Abstract: An innovative type of lithium decahydroborate (Li@B 10 H 14 ) complex with a basketlike complexant of decaborane (B 10 H 14 ) has been designed using quantum mechanical methods. As Li atom binds in a handle fashion to terminal electrophilic boron atoms of the decaborane basket, its NBO charge q (Li) is found to be 0.876, close to +1. This shows that the Li atom has been ionized to form a cation and an anion at the open end of B 10 H 14 . The most fascinating feature of this Li doping is its loosely bound valence electron, which has been pulled into the cavity of the B 10 H 14 basket and become diffuse by the electron-deficient morphological features of the open end of the B 10 H 14 basket. Strikingly, the first hyperpolarizability ( 0 ) of Li@B 10 H 14 is about 340 times larger than that of B 10 H 14 , computed to be 23 075 au (199 × 10 -30 esu) and 68 au, respectively. Besides this, the intercalation of the Li atom to the B 10 H 14 basket brings some distinctive changes in its Raman, 11 B NMR, and UV-vis spectra along with its other electronic properties that might be used by the experimentalists to identify this novel kind of Li@B 10 H 14 complex with a large electro- optical response. This study may evoke the possibility to explore a new thriving area, i.e., alkali metal-boranes for NLO application. Introduction A large number of reports have been presented up until now on nonlinear optical (NLO) materials with different conventional strategies to enhance the NLO response. 1 These strategies mainly include the use of molecules with extended π-electron systems, 2a,b the planar donor-π-conjugated bridge-acceptor (D-π-A) model, 2c,d twisted π-electron systems, 2e octupolar molecules, 3a-c enhanced push-pull effects, 3d,e bond length alternation (BLA) theory, 4a incorporation of ligated metal into the organic compounds, 4b-e and so forth. Similarly, Li and co-workers have made many fascinating reports on NLO material with Li-doped electride/salt complexes. 5 These alkali-metal-doped complexes have shown a significantly large NLO response, and the Li valence electron played a crucial role in the large NLO value of these compounds. 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Published on Web 07/30/2009 10.1021/ja9032023 CCC: $40.75  2009 American Chemical Society J. AM. CHEM. SOC. 2009, 131, 11833–11840 9 11833 Downloaded by NORTHEASTERN NORMAL UNIV LIB on August 22, 2009 Published on July 30, 2009 on http://pubs.acs.org | doi: 10.1021/ja9032023