Theoretical Study on Realization of Nonequilibrium Reaction Field Analogs by Unique Aggregated Coordination Space

本课题以微孔配位聚合物为例，基于分子轨道理论和密度泛函理论，对材料中孔隙的微观性质进行了估算和澄清。[结果]1)微孔配位聚合物CPL-1的微观性质在万有力场(UFF)的基础上，我们重新标定了02的力场参数，以便较好地描述CPL-1中02二聚体在纳米通道中的梯形结构等热力学行为。然后，02-02相互作用的有效势被表示为V02-02，它是范德华相互作用VvdW和四极相互作用VEQQ的总和。通过将V02-02拟合到从头算数据，用于OGG…的一组参数D0-0、RE0-0和Q0得到了较多的02分子的En原子，分别为59.4762 K，5.9943 a0和-0.2227 e。另外，利用Gaussian03可以在MP2/6-31G+(D)的理论水平上直接得到-0.2518 e，从而合理地再现了02分子的四极矩。2)CPL-2中特定聚合的反应机理可以理解，使用UFF的分子力学优化结构也应该重现CPL-2中丙酸甲酯(MP)单体和羧酸盐部分中的两个氧原子之间的特定氢键相互作用。MP分子中的-C≡CH基团明显朝向孔壁上的羧基氧原子，乙酰氢原子和氧原子距离足够近，可以形成有效的氢键(2.8和2.9Å)，这与实验结果是一致的.参考文献3给出了CPL-2中纳米通道中随机排列的MP分子的示意图，这些分子实际上是紧密堆积的，用于控制立体结构(顺式和反式链序列)。化学。SoC。(2)(A)T.Uemura，R.Kitaura，Y.Ohta，M.Nagaoka，S.Kitagawa，Angew.化学。2006年，118,4218；(B)Angew。化学。内部艾德。2006年，45,4112。(3)M.Nagaoka，Y.Ohta和H.Hitomi，Coord。化学。Rev.，2007,251,2522.较少

In this project, taking microporous coordination polymers as an example, we estimate and clarify the microscopic properties of the pores in materials on the basis of molecular orbital (M0) theory and density functional theory (DFT). Further, through molecular mechanical (MM) and monte carlo (MC) simulation, we will survey the guideline to design the coordination space by investigating the correspondence between the macroscopic and the microscopic ones.[Results] 1) Microscopic properties of microporous coordination polymer CPL-1 On the basis of Universal Force Field (UFF), we recalibrated the force-field parameters of 02 for the purpose to describe the thermodynamic behaviors satisfactorily, e.g., the ladder structure of 02 dimers in nanochannels in CPL-1. Then, the effective potential of 02-02 interaction was expressed as V02-02, a summation of van der Waals VvdW and quadrupole interaction VEQQ. By fitting V02-02 to the ab initio data, a set of parameters D0-0, Re0-0 and q0 for an oxyg … More en atom of 02 molecule were obtained, i. e., 59.4762 K, 5.9943 a0 and -0.2227 e, respectively.In addition, q0 could be obtained directly as -0.2518 e at the MP2/6-31G+(d) level of theory by utilizing Gaussian03, so that it could reproduce reasonably the quadrupole moment of 02 and, then, corresponds to the fitting q0 value.2) Reaction mechanism in specific polymerization in CPL-2 It can be understood that the molecular mechanically optimized structure by using the UFF should also reproduce a specific hydrogen-bonding interaction between an methyl propiolate (MP) monomer and two oxygen atoms in the carboxylate moiety in CPL-2. The -C ≡ CH group of MP is clearly oriented towards the carboxylate oxygen atoms on the pore wall, and the acetylenic hydrogen atom and the oxygen atoms are close enough for an efficient hydrogen bonding (2.8 and 2.9 Å), which is consistent with the experimental results. A schematic illustration is shown in Ref.3 for randomly-aligned MP molecules in the nanochannel in CPL-2, which are found closely-packed in fact for controlling the stereostructure(the cis and trans chain sequence).[References](l) Y. Ohta, H. Hitomi, M. Nagaoka, R. Matsuda and S. Kitagawa, J. Amer. Chem. Soc. 2007, submitted.(2) (a) T. Uemura, R. Kitaura, Y. Ohta, M. Nagaoka, S. Kitagawa, Angew. Chem. 2006, 118, 4218; (b) Angew. Chem. Int. Ed. 2006, 45, 4112.(3) M. Nagaoka, Y. Ohta and H. Hitomi, Coord. Chem. Rev., 2007, 251, 2522. Less