Syntheses and Luminescent Properties of 3,5-Diphenylpyrazolato-Bridged Heteropolynuclear Platinum Complexes. The Influence of Chloride Ligands on the Emission Energy Revealed by the Systematic Replacement of Chloride Ligands by 3,5-Dimethylpyrazolate
Syntheses and Luminescent Properties of 3,5-Diphenylpyrazolato-Bridged Heteropolynuclear Platinum Complexes. The Influence of Chloride Ligands on the Emission Energy Revealed by the Systematic Replacement of Chloride Ligands by 3,5-Dimethylpyrazolate
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DOI：
10.1021/ic202663q
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发表时间：
2012-08-06
影响因子：
4.6
通讯作者：
Umakoshi, Keisuke
中科院分区：
文献类型：
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作者：
Akatsu, Seiji;Kanematsu, Yasunori;Umakoshi, Keisuke
与3，5-二苯基吡唑的异多核Pt-II络合物[Pt 2Ag 4（mu-Cl）（2）（mu-Ph（2）pz）（6）]（3），[Pt 2Ag 2Cl 2（mu-Ph（2）pz）（4）（Ph（2）pzH）（2）]（4），[Pt 2Cu 2Cl 2（mu-Ph（2）pz）（4）（Ph（2）pzH）（2）]（5），[Pt 2Ag 4（mu-Cl）（mu-Me（2）pz）（mu-Ph（2）pz）（6）]（7），和[Pt_2Ag_4（mu-Me（2）pz）（2）（mu-Ph（2）pz）（6）]（8）的配合物。这些络合物是发光的，除了5在室温下处于固态时分别发射红-橙子（3）、橙子（4）、黄-橙子（7）和绿色（8）光。系统的红移的发射能量与氯化物配体的数量进行了观察为3，7，和8。密度泛函理论计算表明，以Pt_2Ag_4为核的杂六核配合物3、7和8的最高占据分子轨道（HOMO）和HOMO-1主要由Pt-II的do轨道和Ph（2）pz配体的pi轨道组成，而这些配合物的最低未占分子轨道（LUMO）主要由两个Pt-Ⅱ中心的6p和四个Ag-Ⅱ中心的5 p的同相结合组成。很可能3、7和8的发射归因于来自Pt-2（d）/pi -> Pt 2Ag 4跃迁的发射态，其发射能量取决于氯配体与吡唑基配体的比率。
Heteropolynuclear Pt-II complexes with 3,5-diphenylpyrazolate [Pt2Ag4(mu-Cl)(2)(mu-Ph(2)pz)(6)] (3), [Pt2Ag2Cl2(mu-Ph(2)pz)(4)(Ph(2)pzH)(2)] (4), [Pt2Cu2Cl2(mu-Ph(2)pz)(4)(Ph(2)pzH)(2)] (5), [Pt2Ag4(mu-Cl)(mu-Me(2)pz)(mu-Ph(2)pz)(6)] (7), and [Pt2Ag4(mu-Me(2)pz)(2)(mu-Ph(2)pz)(6)] (8) have been prepared and structurally characterized. These complexes are luminescent except for 5 in the solid state at an ambient temperature with emissions of red-orange (3), orange (4), yellow-orange (7), and green (8) light, respectively. Systematic red shift of the emission energies with the number of chloride ligands was observed for 3, 7, and 8. DFT calculations indicate that the highest occupied molecular orbital (HOMO) as well as HOMO-1 of the heterohexanuclear complexes, 3, 7, and 8, having Pt2Ag4 core, mainly consist of do orbital of Pt-II and pi orbitals of Ph(2)pz ligands, while the lowest unoccupied molecular orbital (LUMO) of these complexes mainly consists of in-phase combination of 6p of two Pt-II centers and 5p of four Ag-I centers It is likely that the emissions of 3, 7, and 8 are attributed to emissive states derived from the Pt-2(d)/pi -> Pt2Ag4 transitions, he emission energy of which depends on the ratio of chloride ligands to pyrazolate ligands.