Polyhedral Oligomeric Silsesquioxane (POSS) cages with endohedral metal hydrides

1. Polyhedral OligomericSilsesquioxane (POSS) cages with endohedral metal hydrides Xiqiao Wang, John Corn, Frank Hagelberg Department of Physics and Astronomy East Tennessee State University Johnson City, TN 37614 System Method ΔE [Hartree] RuH2@T10 MP2/CEP-121G -0.024 ~ -0.030 PdH2@T10MP2/CEP-121G -0.007 OsH2@T10MP2/CEP-121G -0.012 PtH2@T10 MP2/CEP-121G -0.006 Motivation Polyhedral OligomericSilsesquioxane (POSS) cages are of major interest as building blocks for nano-structured hybrid materials and nanocomposites [1-3]. POSS molecules may be employed to increase the interfacial area and to tune domain distances in solar cells based on conjugated polymers and fullerenes [1]. In this contribution, we investigate encapsulation of metal hydrides as a means to alter the energetic and electronic properties of three basic POSS cages ( Tn with n = 8, 10, 12) in a controlled way. As an additional benefit, POSS cages with internal metal hydrides might prove to be efficient as novel media of hydrogen storage. AlH3 , a light metal-hydride (left: Al crystals, right: AlH3 crystals) Fullerene Cages L.Gagliardi performed a computational study of metal-hydrides encapsulated in within fullerenes, such as ZrH16 @ C60 and 2TiH16 @ C114[4]. Method The interaction between metal hydride cores and POSS cages was explored by using various ab initioand density functional theory (DFT) techniques [5], with ab initio procedures ranging from HF (Hartree-Fock) to MP2 (Moeller-Plesset perturbation theory at second order). A variety of metal-hydrides could be stored in T12 cages. However, the more conventional T8 cage is more easily fabricated. For MHm molecules inside the T8 and T10 cages, no stability was found for m>2 . For m=2, cage symmetry change associated with elongation along the MH2 axis was found to occur in T8 cage. PtH4 within T12 Optimization performed using frequency analysis at the B3LYP/CEP-31G level Some common structures of MH2@T10 complexes Due to the size restriction associated with T8,no systems of the form MHm@T8 with m > 2 were found to converge. Some periodic arrangements of T8 and MH2@T8 were included and proven to be stable: FeH2 within T8 Results were found at the HF/CEP-121G level. Geometric optimizations were confirmed using MP2 and B3LYP. • Summary • A wide variety of POSS cages with enclosed metal hydrides were shown to be stable by ab initio computation. For RuH2, PdH2, OsH2 , PtH2 encapsulation into T10 was found to be an exothermal process. • An effort to analyze POSS polymers with endohedral metal hydrides was initialized. Results Equilibrium structures were obtained for systems of the form MHm@Tn [(SiO3/2H)n], with m = 2, 3, 4, n = 8, 10, 12, and M = transition metal elements in Group IVB, VIB, VIII, IIB. The potential surface inside the less studied T12 cage turned out to be relatively flat, and equilibrium geometries were obtained for a wide range of large metal hydrides. Zero-point corrected stabilization energies ΔE for T10 based systems were found to be negative, corresponding to an exothermal encapsulation process, in 4 cases: References: [1] F.Wang, X.Lu, C.He, J.Mat.Chem. 21, 2775 (2011) [2] D. Hossain, F.Hagelberg, C.Pittman, S.Saebo, J.Inorg. Org.Pol.Mat.20, 1574 (2010) [3] D. Hossain, C. Pittman Jr., F. Hagelberg, S. Saebo, J.Phys.Chem.C, 112, 16070 (2008) [4] L.Gagliardi, J.Chem.Theo.Comp. 1, 1172 (2005) [5] M.J.Frisch et al. Gaussian, Rev. B.01, Gaussian Inc., Wallingford, CT (2004) Acknowledgment: Support by TN-SCORE (NSF EPS 1004083) is gratefully acknowledged.