By employing functional ligand 3,6-bis（3,5-dimethyl-lH-pyrazol-4-yl）-9-methyl- 9H-carbazole, a novel luminescent Ni complex has been obtained. Its structure was characterized by single-crystal X-ray diffraction anal...By employing functional ligand 3,6-bis（3,5-dimethyl-lH-pyrazol-4-yl）-9-methyl- 9H-carbazole, a novel luminescent Ni complex has been obtained. Its structure was characterized by single-crystal X-ray diffraction analysis. Crystal data： monoclinic, space group P2/c, a = 13.4224（18）, b = 13.759（2）, c = 8.0633（17）/~, fl = 96.448（3）~, C23H23NsNi（NO3）2, M,. = 552.19, V = 1479.7（4） A3, Z = 2, Dc = 1.239 g/cm3,/ffMoKa） = 0.700 mm-1, F（000） = 572, the final R = 0.0566 and wR = 0.1336 for 1638 observed reflections with I 〉 2a（/）. X-ray analysis indicates that each metal center coordinates with two N and two H atoms in tetrahedral interaction geometry. Weak interaction between Ni and N atom of pyrazole ligand and agostic bond （Ni...H-N interaction） play important roles in the formation of the 2-dimension framework. Significantly, this framework could pack into a tubular channel with NO3 anions trapped inside.展开更多
在UB3LYP/6-311++G(3df,3pd)水平下,详细研究了Ni活化NH3分子的单重态和三重态势能面,并用分子中的原子量子理论(Quantum Theory of Atom-in-Molecular,QTAIM)计算了势能面上所有驻点的性质.计算结果表明,单重态势能面有两条反应途径,...在UB3LYP/6-311++G(3df,3pd)水平下,详细研究了Ni活化NH3分子的单重态和三重态势能面,并用分子中的原子量子理论(Quantum Theory of Atom-in-Molecular,QTAIM)计算了势能面上所有驻点的性质.计算结果表明,单重态势能面有两条反应途径,而三重态势能面仅有一条反应途径.第一个N-H断开的活化能较低,为99.96kJ/mol,活化自由能为100.86kJ/mol,在常温下就可以进行;第二个N-H键断裂所需能量高达200kJ/mol,不容易进行.在合适温度下,Ni可以活化NH3得到三重态HNiNH2,这表明Ni可以作为活化NH3分子的良好催化剂.展开更多
基金supported by the Natural Science Foundation of Zhejiang Province(Y5080308)
文摘By employing functional ligand 3,6-bis（3,5-dimethyl-lH-pyrazol-4-yl）-9-methyl- 9H-carbazole, a novel luminescent Ni complex has been obtained. Its structure was characterized by single-crystal X-ray diffraction analysis. Crystal data： monoclinic, space group P2/c, a = 13.4224（18）, b = 13.759（2）, c = 8.0633（17）/~, fl = 96.448（3）~, C23H23NsNi（NO3）2, M,. = 552.19, V = 1479.7（4） A3, Z = 2, Dc = 1.239 g/cm3,/ffMoKa） = 0.700 mm-1, F（000） = 572, the final R = 0.0566 and wR = 0.1336 for 1638 observed reflections with I 〉 2a（/）. X-ray analysis indicates that each metal center coordinates with two N and two H atoms in tetrahedral interaction geometry. Weak interaction between Ni and N atom of pyrazole ligand and agostic bond （Ni...H-N interaction） play important roles in the formation of the 2-dimension framework. Significantly, this framework could pack into a tubular channel with NO3 anions trapped inside.
文摘在UB3LYP/6-311++G(3df,3pd)水平下,详细研究了Ni活化NH3分子的单重态和三重态势能面,并用分子中的原子量子理论(Quantum Theory of Atom-in-Molecular,QTAIM)计算了势能面上所有驻点的性质.计算结果表明,单重态势能面有两条反应途径,而三重态势能面仅有一条反应途径.第一个N-H断开的活化能较低,为99.96kJ/mol,活化自由能为100.86kJ/mol,在常温下就可以进行;第二个N-H键断裂所需能量高达200kJ/mol,不容易进行.在合适温度下,Ni可以活化NH3得到三重态HNiNH2,这表明Ni可以作为活化NH3分子的良好催化剂.
