TY - JOUR
T1 - Platinum(II) complexes with spatially encumbered chelates; syntheses, structure and photophysics
AU - Hsieh, Hsi-Ying
AU - Lin, Chen-Huey
AU - Tu, Guan-Min
AU - Chi, Yun
AU - Lee, Gene-Hsiang
PY - 2009/10/15
Y1 - 2009/10/15
N2 - 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.
AB - 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.
KW - Bond strain
KW - Photophysics
KW - Platinum(II) complexes
KW - Triazolate
KW - X-ray crystal structures
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U2 - 10.1016/j.ica.2009.06.041
DO - 10.1016/j.ica.2009.06.041
M3 - RGC 21 - Publication in refereed journal
SN - 0020-1693
VL - 362
SP - 4734
EP - 4739
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
IS - 13
ER -