Platinum(II) complexes with spatially encumbered chelates; syntheses, structure and photophysics |
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Authors: | Hsi-Ying Hsieh Chen-Huey Lin Yun Chi |
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Institution: | a Department of Food Nutrition, Chung Hwa College of Medical Technology, Tainan 717, Taiwan b Department of Chemistry, National Tsing Hua University, Hsinchu 300, Taiwan c Department of Chemistry, National Taiwan University, Taipei 106, Taiwan |
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Abstract: | Treatment of the spatially congested 5-(6-methylpyridin-2-yl)-3-trifluoromethyl-1,2,4-triazole (fmptzH) chelate with K2PtCl4 in basic media gave a pale-yellow complex Pt(fmptz)2] (1), for which the single crystal X-ray diffraction study showed a highly distorted square-planar coordination geometry with one N-Pt-N vector significantly deviated from linearity. This complex undergoes slow equilibration in refluxing THF to afford a dinuclear complex Pt(fmptz)(μ-fmptz)]2 (2), showing reversible transformation of one fmptz chelate to the distinctive bridging mode. Synthesis of the less spatially congested, heteroleptic complexes Pt(fppz)(fmptz)] (3) and Pt(iqbpz)(fmptz)] (4) were successfully achieved by combination of Pt(fppzH)Cl2] and Pt(iqbpzH)Cl2] with one equiv. of fmptzH ligand under similar condition, fppzH = 5-(2-pyridyl)-3-trifluoromethyl-pyrazole and iqbpzH = 5-(1-isoquinolyl)-3-tert-butyl-pyrazole. Only the derivative 4 was found to be weakly emissive in both fluid and solid states at room temperature. |
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Keywords: | Platinum(II) complexes Triazolate Bond strain Photophysics X-ray crystal structures |
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