A New Class of Cuprous Bromide Cluster-Based Hybrid Materials: Direct Observation of the Stepwise Replacement of Hydrogen Bonds by Coordination Bonds

作者：Zhang Xian Ming^*; Hou Juan Juan; Guo Cai Hong; Li Chun Fang

来源：Inorganic Chemistry, 2015, 54(2): 554-559.

DOI：10.1021/oc5024168

Although a variety of functional metalorganic frameworks (MOFs) have been synthesized, post-modified, and applied in various areas, there is little knowledge about how molecular cluster building units are stepwise evolved into MOFs via intermediates. Coordination bonds are generally stronger than hydrogen bonds, and thus equivalent replacement of X-H...Y hydrogen bonds by X-M-Y coordination bonds can transform hydrogen bond networks into MOFs. In this work, solvothermal in situ reduction reactions of CuBr2 and 1,4-diazoniabicyclo[2,2,2]octane (DABCO) generated a myriad of tunable photoluminescent cuprous body-centered cubic bromide cluster-based networks with the general formula [Cu4+xH4-xBr6(DABCO)4](HCO2)(2).S (x = 0, 0.56, 0.81, 1.27, 1.39, 2.56, 2.78, and 4 for compounds 1-8, respectively). All of these compounds crystallize in the cubic space group with the largest volume difference being only 5.2%, but they belong to three remarkably different kinds of crystals. Complex 1 is a molecular crystal and consists of tetrahedral [Cu4Br6(HDABCO)(4)](2+) clusters with monodentate HDABCO groups that are supported via NH...Br synthons in the hydrogen bond network. Compound 8 is a [Cu8Br6](2+) cube cluster-based MOF with bridged DABCO ligands. Complexes 27 are seemingly impossible Cu/H-substituted solid solutions of 1 and 8. The Cu-Br framework components in 18 are Cu4Br6, Cu4.56Br6, Cu4.81Br6, Cu5.27Br6, Cu5.39Br6, Cu6.56Br6, Cu6.78Br6, and Cu8Br6, respectively. Crystallization kinetics studies revealed that the [Cu4Br6(HDABCO)(4)](2+) cluster-based hydrogen bond network (1) was initially formed such that NH...Br hydrogen bonds could be stepwise replaced by N-Cu-Br coordination bonds to form the [Cu8Br6](2+) cube cluster-based MOF (8) via solid solutions. These observations directly reveal the equivalence and transformation between the N-H...Br hydrogen bond and the N-Cu-Br coordination bond and the evolutionary mechanism of a molecular crystal to a MOF via solid solutions, which is of fundamental importance in materials but has never before been revealed. DFT calculations suggest that equivalent replacement of a N-H...Br hydrogen bond by a NCuBr coordination bond is exothermic and exergonic, which also supports the transformation from molecule 1 to MOF 8.

• 出版日期2015-1-19
• 单位山西师范大学