Ligand Size Effect on PdLn Oxidative Addition with Aryl Bromide： A DFT Study

The process and mechanism of the ligand volume controlled Pd（PR3）2 （PR3=PH3, PMe3, and PtBu3） oxidative addition with aryl bromide were investigated, using density functional theory method with the conductor-like screening model. Association pathway and dissocia-tion pathway were investigated by the comparison of several energies. The cleavage energy of Pd（PR3）2 complex was calculated, as well as the oxidative addition reaction barrier energy of Pd（PR3）n （n=1,2） with aryl bromide in N,N-dimethylformamide solvent. This study proved that the ligands volume possessed a great impact on the mechanism of oxidative addition： less bulky ligand palladium associated with aryl bromide via two donor ligands,but larger bulky ligand palladium coordinated via monoligand.

Solid-state phase transformations toward a metal-organic framework of 7-connected Zn_(4)0 secondary building units

In the development of metal-organic frameworks(MOFs),secondary building units(SBUs)have been utilized as molecular modules for the construction of nanoporous materials with robust structures.Under solvothermal synthetic conditions,dynamic changes in the metal coordination environments and ligand coordination modes of SBUs determine the resultant product structures.Alternatively,MOF phases with new topologies can also be achieved by post-synthetic treatment of as-synthesized MOFs via the introduction of acidic or basic moieties that cause the simultaneous cleavage/reformation of coordination bonds in the solid state.In this sense,we studied the solid-state transformation of two ndc-based Zn-MOFs(ndc=1,4-naphthalene dicarboxylate)with different SBUs but the same pcu topology to another MOF with sev topology.One of the chosen MOFs with pcu nets is[Zn_(2)(ndc)_(2)(bpy)]_(n)(bpy=4,4,-bipyridine),(6C_(bpy)-MOF)consisting of a 6-connected pillared-paddlewheel SBU,and the other is IRMOF-7 composed of 6-connected Zn40(C 00)6 SBUs and ndc.Upon post-structural modification,these pcu MOFs were converted into the same MOF with sev topology constructed from the uncommon 7-connected Zri_(4)O(COO)_(7)SBU(7C-MOF).The appropriate post-synthetic conditions for the transformation of each SBUs were systematically examined.In addition,the effect of the pillar molecules in the pillared-paddlewheel MOFs on the topology conversion was studied in terms of the linker basicity,which determines the inertness during the solid-state phase transformation.This post-synthetic modification approach is expected to expand the available methods for designing and synthesizing MOFs with controlled topologies.