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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Synthesis and photophysical properties of silicon phthalocyanines with axial siloxy ligands bearing alkylamine termini
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Synthesis and photophysical properties of silicon phthalocyanines with axial siloxy ligands bearing alkylamine termini

机译：带有烷基胺末端的轴向甲硅烷氧基配体的硅酞菁的合成及光物理性质

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摘要

Eleven silicon phthalocyanines which can be grouped into two homologous series [SiPc[OSi(CH3)(2)(CH2)(n)N-(CH3)(2)](2), n = 1-6 (series 1), and SiPc[OSi(CH3)(2)(CH2)(3)N((CH2)(n)H)(2)](2), n = 1-6 (series 2)] as well as an analogous phthalocyanine, SiPc[OSi(CH3)(2)(CH2)(3)NH2](2), were synthesized. The ground state absorption spectra, the triplet state dynamics, and singlet oxygen quantum yields of 10 of these phthalocyanines were measured. All compounds displayed similar ground state absorption spectral properties in dimethylformamide solution with single Q band maxima at 668 +/- 2 nm and B band maxima at 352 +/- 1 nm. Photoexcitation of all compounds in the B bands generated the optical absorptions of the triplet states which decayed with lifetimes in the hundreds of microseconds region. Oxygen quenching bimolecular rate constants near 2 x 10(9) M-1 s(-1) were measured, indicating that energy transfer to oxygen was exergonic. Singlet oxygen quantum yields, Phi(Delta), were measured, and those phthalocyanines in which the axial ligands are terminated by dimethylamine residues at the end of alkyl chains having four or more methylene links exhibited yields near >= 0.35. Others gave singlet oxygen quantum yields near 0.2, and still others showed singlet oxygen yields of < 0.1. The reduced singlet oxygen yields are probably caused by a charge transfer quenching of the (1)pi pi* state of the phthalocyanine by interaction with the lone pair electrons on the nitrogen atoms of the amine termini. In some cases, these can approach and interact with the electronically excited pi-framework, owing to diffusive motions of the flexible oligo-methylene tether.
机译：可以分为11个同源系列的11种硅酞菁硅[SiPc [OSi（CH3）（2）（CH2）（n）N-（CH3）（2）]（2），n = 1-6（系列1，和SiPc [OSi（CH3）（2）（CH2）（3）N（（CH2）（n）H）（2）]（2），n = 1-6（系列2）]以及类似的酞菁合成了SiPc [OSi（CH3）（2）（CH2）（3）NH2]（2）。测量了10种这些酞菁的基态吸收光谱，三重态动力学和单重态氧量子产率。所有化合物在二甲基甲酰胺溶液中显示出相似的基态吸收光谱特性，在668 +/- 2 nm处有一个Q值最大值，在352 +/- 1 nm处有一个B值最大值。 B带中所有化合物的光激发产生三重态的光学吸收，该三重态在数百微秒的区域内随着寿命而衰减。测量了在2 x 10（9）M-1 s（-1）附近的氧猝灭双分子速率常数，这表明向氧的能量转移是能量的。测量了单重态氧量子产率PhiΔ，并且其中轴向配体在具有四个或更多个亚甲基键的烷基链的末端被二甲胺残基终止的那些酞菁具有> 0.35的产率。其他人给出的单重态氧量子产率接近0.2，而另一些人给出的单重态氧量子产率＜0.1。单线态氧产量的降低可能是由于与胺末端氮原子上的孤对电子相互作用而使酞菁的（1）pi pi *态发生电荷转移猝灭所致。在某些情况下，由于柔性低聚亚甲基系链的扩散运动，它们可以接近电子激发的pi框架并与之相互作用。

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