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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Temperature dependence of the crystal structure and luminescence properties of [Pt{4'-(omicron-ClC_6H_4)trpy}Cl]SbF_6(trpy = 2,2':6',2'-terpyridine)
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Temperature dependence of the crystal structure and luminescence properties of [Pt{4'-(omicron-ClC_6H_4)trpy}Cl]SbF_6(trpy = 2,2':6',2'-terpyridine)

机译：[Pt {4'-（omicron-ClC_6H_4）trpy} Cl] SbF_6（trpy = 2,2'：6'，2“ -terpyridine）的晶体结构和发光特性的温度依赖性

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摘要

The synthesis and characterisation of 4'-(2"'-chlorophenyl)-2,2':6',2"-terpyridine [4'-(omicron-ClC_6H_4)trpy] and [Pt{4'-(omicron-QC_6H_4)trpy}C1]SbF_6 are described.An X-ray crystal structure determination of the salt reveals columns of cations and anions with the cations stacked parallel and head-to-tail.At 295 K the Pt ...Pt distances alternate between 3.374(1)and 3.513(1)A while the perpendicular separation between the mean planes comprising the platinum and three bonded nitrogen atoms remains constant at 3.35 A.As evidenced by crystal structure determinations at 260,240 and 180 K,the shorter Pt ...Pt distances become systematically shorter and the longer Pt ...Pt distances become systematically longer as the temperature of the crystal is lowered.Structural evidence is presented that shows that this trend is a consequence of the more closely separated platinum atoms slipping into line with respect to a perpendicular to the above planes;at the same time the more widely separated platinum atoms fall out-of-line as the temperature is lowered.Emission spectra measured on a polycry stalling sample of the salt at 40 K intervals from 280 to 80 K comprise a single,asymmetric and featureless band [lambda_max~em = 609 nm at 280 K] that systematically increases in intensity as the temperature is lowered.There is a slight blue shift in the wavelength of the emission maximum as the temperature is lowered to 240 K but,below this temperature,the emission maximum gradually and systematically shifts to the red [lambda_max~em= 642 nm at 80 K].This behaviour is rationalised in terms of ~3MMLCT emission,the energy of which being determined by subtle changes in the extent of d_(z~2-)d~(z~2)orbital overlap between adjacent platinum atoms separated by the shorter distance on one hand,and between platinum atoms separated by the longer distance on the other.
机译：4'-（2“'-氯苯基）-2,2'：6'，2”-吡啶[4'-（omicron-ClC_6H_4）trpy]和[Pt {4'-（omicron-QC_6H_4） } trpy} C1] SbF_6。盐的X射线晶体结构测定表明，阳离子和阴离子的列平行且头对尾堆叠。在295 K时，Pt ... Pt距离在3.374之间交替（1）和3.513（1）A，而包含铂和三个键合氮原子的平均平面之间的垂直间距保持恒定在3.35 A.260,240和180 K的晶体结构确定证明，Pt ... Pt较短随着晶体温度的降低，Pt距离逐渐变短，Pt ... Pt距离变长，系统地变长。结构证据表明，这种趋势是由于铂原子相对分离得更紧密而滑移成线的结果。垂直于上述平面的a;与此同时，分离的p随着温度的降低，原子上的原子脱离线外。在盐的多晶失速样品上以280至80 K的40 K间隔测量的发射光谱包括一个单一的，不对称且无特征的谱带[lambda_max〜em = 609 nm。 280 K]会随着温度降低而系统地增加强度。随着温度降低到240 K，发射最大值的波长会有轻微的蓝移，但在此温度以下，发射最大值逐渐并系统地移到红色[lambda_max〜em = 642 nm在80 K]。此行为在〜3MMLCT发射方面得到了合理化，其能量由d_（z〜2-）d〜（z〜2）范围内的细微变化确定。一方面，相邻的铂原子之间以较短的距离隔开，另一方面，之间的铂原子之间的轨道重叠。

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