Synthesis and nonlinear optical, photophysical, and electrochemical properties of subphthalocyanines
Synthesis and nonlinear optical, photophysical, and electrochemical properties of subphthalocyanines
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DOI：
10.1021/ja980508q
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发表时间：
1998-12-16
影响因子：
15
通讯作者：
Zyss, J
中科院分区：
文献类型：
--
作者：
del Rey, B;Keller, U;Zyss, J
利用三卤化硼诱导邻苯二腈在1-氯萘中被充分取代的衍生物的环三聚反应，合成了可溶于含有多种供体和受体取代基的有机溶剂的新型硼（III）亚酞菁（SubPcs）。1,2-二氨基苯衍生物上取代基的选择考虑了路易斯酸BCl3对许多官能团的高反应性。考虑到这个限制。我们开始合成具有碘、硝基、烷基或芳基硫基、烷基或芳基磺基的邻苯二腈，这些基在所需的反应条件下足够稳定，并且还提供了一组容易获得的受体/供体取代基。这些化合物的二次和三次超极化率以及它们的线性光学和电化学性质已经通过几种技术进行了测量，包括EFISH（两个波长）、HRS和THG、稳态和时间分辨吸收和荧光、激光诱导光声量热法、时间分辨近红外发射光谱和循环伏安法。在1.46 μ m处测得β (HRS)，可以排除多光子诱导荧光的污染。β (HRS)达到很高的值，这明显依赖于替代。取代基的受体特征明显增强，具有最强受体基团的化合物获得的值最高。它们与许多高效的二级化合物相当，甚至优于它们。这些结果的一个主要结果是，适当选择取代基为优化SubPcs的二次响应提供了一条有希望的途径。这种化合物比它们的扩展类似物酞菁更不容易聚集，荧光量子产率约为0.25，低于酞菁的典型量子产率，并且具有更大的三态量子产率。三态寿命在100 μ s的时间范围内，足够长的时间进行高效的氧猝灭。事实上，亚酞菁能敏化单线态分子氧O-2((1)Delta(g))，量子产率从0.23到0.75不等。基态氧化电位与酞菁相似，而还原电位明显偏负；也就是说，它们更难以减少。相比之下，电子激发的亚酞菁比相应的酞菁更容易被氧化约500 mV，这导致较低的光稳定性，特别是在极性溶剂中。
Novel boron(III) subphthalocyanines (SubPcs) soluble in organic solvents containing a variety of donor and acceptor substituent groups have been synthesized by boron trihalide-induced cyclotrimerization of adequately substituted derivatives of phthalonitrile in 1-chloronaphthalene. The choice of the substituents on the 1,2-dicyanobenzene derivatives has been made taking into account the high reactivity of the Lewis acid BCl3 toward many functional groups. Considering this limitation. we set out to synthesize phthalodinitriles equipped with iodo, nitro, alkyl- or arylthio, alkyl- or arylsulfonyl groups that are sufficiently stable under the required reaction conditions and also provide an easily accessible set of acceptor/donor substituents. The quadratic and cubic hyperpolarizabilities of these compounds as well as their linear optical and electrochemical properties have been measured by several techniques, including EFISH (at two wavelengths), HRS, and THG, steady-state and time-resolved absorption and fluorescence, laser-induced optoacoustic calorimetry, time-resolved near-infrared emission spectroscopy, and cyclic voltammetry. beta(HRS) has been measured at 1.46 mu m, where the contamination from the multiphoton-induced fluorescence can be ruled out. beta(HRS) reachs high values that markedly depend on substitution. It shows a clear enhancement with the acceptor character of the substituents, the highest values being obtained for the compounds bearing the strongest acceptor groups. They are comparable or even superior to many efficient second-order compounds. A main outcome of these results is that an adequate choice of the substituents offers a promising route for optimization of the quadratic response of the SubPcs. This kind of compounds is less prone to aggregation than their expanded analogues, the phthalocyanines, fluoresces with quantum yields ca. 0.25, lower than those typical for phthalocyanines, and has larger triplet quantum yields. The tripler-state lifetime is in the 100-mu s time range, long enough for efficient oxygen quenching. Indeed, subphthalocyanines sensitize singlet molecular oxygen, O-2((1)Delta(g)), with quantum yields ranging from 0.23 to 0.75. The ground-state oxidation potentials an similar to those of phthalocyanines, while the reduction potentials are clearly more negative; i.e., they are more difficult to reduce. In contrast, electronically excited subphthalocyanines are more easily oxidized than the corresponding phthalocyanines by ca. 500 mV which results in lower photostability, especially in polar solvents.