SelfAssembling Capsules Molecular Behavior in Small Spaces Rebek

研究計畫主題 Self-Assembling Capsules 的理論計算 “Molecular Behavior in Small Spaces“ Rebek, J. , Jr. Acc. Chem. Res. 2009, 42, 1660. 2

Host–guest chemistry The Nobel Prize in Chemistry 1987 Molecular encapsulation Supramolecular chemistry Synthesizing crown ethers The pictures of the laureates are from the web site of Nobelprize. org. 3

First Soluble Capsule • 1989 年，Cram 等人合成出了第一個可溶解於有 機溶劑的 carceplex，結構上下兩側的 phenethyl group (Ph. CH 2 -) 增加了 carceplex 的溶解性。 Cram 將其溶解至 chlorofom，並透過 1 H NMR 和 13 C NMR 分析 guest 在 capsule 內部空間的動態行 為。 the rates of rotation about the C-N bond of amide: the first carceplex in 1985 the first soluble carceplex in 1989 for (CH 3)2 NCHO, vacuum > interior phase > solution for (CH 3)2 NCOCH 3, vacuum > solution > interior phase J. Am. Chem. Soc. 1989, 111, 4527. 6

Self-Assembling Capsule • 1998 年 Rebek 參考 Cram 等人合成 capsule 的步驟， 以 resorcinarene 和 imide 合成出一個新型的 cavitand。此一新型的 cavitand 分子，在溶液中大 部分會以 vase-form 兩兩透過氫鍵的方式聚合在一 起，形成一個如膠囊般的分子，其在溶液中穩定 存在的時間約數分鐘至數小時不等。 self-assembling capsule imide resorcinarene cavitand Heinz, T. ; Rudkevich, D. ; Rebek, J. , Jr. Nature 1998, 394, 764 8

Self-Assembling Capsule 所包覆的空間及待測分子 C 14 H 30 tetradecane Acc. Chem. Res. 2009, 42, 1660. 9

Self-Assembling Capsules 的應用 J. Am. Chem. Soc. 2011, 133, 9689. 13

過去 Self-Assembling Capsules 之理論研究 Table. Dimerization Energies in e. V of the Dimers in the Gas Phase and in Capsules at Various Levels of Theory Method CC 　 AA 　 BC 　 AB 　 BB M 06 -2 X/6 -31 G(d, p) 0. 77 > 0. 71 > 0. 60 > 0. 58 > 0. 51 > 0. 47 Oniom-M 06 -2 X/6 -31 G(d, p) in capsule 0. 74 > 0. 63/0. 65 > 0. 58/0. 57 > 0. 55/0. 54 > 0. 46 > 0. 43/0. 44 Oniom-MP 2/6 -31 G(d, p) in capsule 0. 57/0. 56 > 0. 51/0. 50 > 0. 48/0. 46 > 0. 44 > 0. 38/0. 37 > 0. 36/0. 37 Oniom-[high layer] b All low layers are the capsules calculated at PM 6 level c All convergence problems denoted by “ - ” d Trans/cis Petsalakis, I. D. ; et al J. Am. Chem. Soc. 2011, 133, 16977. a 14

Acknowledgment • Prof. Wei-Ping Hu • Our group members. (Dr. Jien-Lian Chen, Dr. Yi-Lun Sun et al. ) • Department of Chemistry & Biochemistry, National Chung Cheng University • National Center for High-Performance Computing 25

Thanks for your attention 26