Luminescent square-planar platinum(II) complexes with tridentate 3-bis(2-pyridylimino)isoindoline and monodentate N-heterocyclic ligands.
Luminescent square-planar platinum(II) complexes with tridentate 3-bis(2-pyridylimino)isoindoline and monodentate N-heterocyclic ligands.
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DOI：
10.1039/c1dt10385g
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发表时间：
2011-06
影响因子：
4
通讯作者：
H. Wen;Yuhui Wu;Liang-jin Xu;Li-Yi Zhang;C. Chen;Zhong-Ning Chen
中科院分区：
文献类型：
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作者：
H. Wen;Yuhui Wu;Liang-jin Xu;Li-Yi Zhang;C. Chen;Zhong-Ning Chen
将1，3-双(2-吡啶亚氨基)异吲哚(BPI)前驱体中的配位氯与N-杂环配体(如吡啶、二氮杂氮或菲)取代，合成了一系列铂(II)配合物。这些配合物在液体二氯甲烷溶液中和室温下的固体中都显示出橙色到红色的发光。通过在BPI配体上引入吸电子NO(2)或给电子NH(2)来调节其光物理性质。密度泛函理论计算表明，N-杂环配体取代的铂(II)配合物的发光主要来源于(3)[π→π*(Bpi)](3)IL三重态的激发态，并混有一定的(3)[dπ(Pt)→π*(Bpi)](3)多层螺旋CT性质。与前驱体铂(BPI)Cl相比，N-杂环配体取代的铂(II)配合物的低能吸收和发射都表现出明显的蓝移，这是由于(3)IL态的贡献明显增加，(3)MLCT特征降低。
A series of platinum(II) complexes with 1,3-bis(2-pyridylimino)isoindoline (BPI) derivatives were prepared by substitution of the coordinated Cl in the precursor complex Pt(BPI)Cl with a N-heterocyclic ligand such as pyridine, phthalazine or phenanthridine. These complexes display orange to red luminescence in fluid dichloromethane solutions and in the solid states at room temperature. The photophysical properties were tuned by introducing electron-withdrawing -NO(2) or electron-donating -NH(2) to the BPI ligand. The DFT computational studies suggest that the emission in the N-heterocyclic ligand substituted platinum(II) complexes originates mainly from the (3)[π→π*(BPI)] (3)IL triplet excited state, mixed with some (3)[dπ(Pt)→π*(BPI)] (3)MLCT character. Compared with the precursor Pt(BPI)Cl, both the low-energy absorption and the emission in the N-heterocyclic ligand substituted platinum(II) complexes exhibits a distinct blue-shift due to an obviously enhanced contribution from the (3)IL state and a reduced (3)MLCT character.