Solvent Effects on the Absorption Profile, Kinetic Stability, and Photoisomerization Process of the Norbornadiene–Quadricyclanes System,The Journal of Physical Chemistry C

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Solvent Effects on the Absorption Profile, Kinetic Stability, and Photoisomerization Process of the Norbornadiene–Quadricyclanes System
The Journal of Physical Chemistry C ( IF 3.3 ) Pub Date : 2019-03-14 , DOI: 10.1021/acs.jpcc.9b02111
Maria Quant ₁ , Alice Hamrin ₂ , Anders Lennartson ₁ , Paul Erhart ₂ , Kasper Moth-Poulsen ₁

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Molecular photoswitches based on the norbornadiene–quadricyclane (NBD-QC) couple can be used to store solar energy and to release the stored energy as heat on demand. In this context, the energy storage time as well as the quantum yield of the energy storing reaction are important parameters. Here, we explore for the first time solvent effects on these processes for a series of four NBD-QC compounds in four different solvents with different polarity (acetonitrile, tetrahydrofuran, toluene, and hexane). We show that the energy storage time of the QC forms can vary by up to a factor of 2 when going from the most to the least polar solvent. Moreover, we show that for the norbornadiene derivatives with an asymmetric 1,2 substitution pattern, the quantum yield of conversion is highly solvent dependent, whereas this is not the case for the symmetrically substituted compounds. The spectroscopic observations are further rationalized using classical molecular dynamics (MD) simulations and time-dependent density functional theory (TDDFT) calculations. These demonstrate the importance of vibrational and rotational excitations for obtaining broad-band absorption, which is a prerequisite for capturing a wide range of the solar spectrum.

中文翻译：

溶剂对降冰片二烯-四环烷体系的吸收特性，动力学稳定性和光异构化过程的影响

基于降冰片二烯-四环素（NBD-QC）对的分子光电开关可用于存储太阳能，并根据需要将存储的能量以热量的形式释放。在这种情况下，储能时间以及储能反应的量子产率是重要的参数。在这里，我们首次探讨了溶剂在一系列极性不同的四种不同溶剂（乙腈，四氢呋喃，甲苯和己烷）中对一系列四种NBD-QC化合物的影响。我们表明，当从最大极性溶剂变为最小极性溶剂时，QC形式的能量存储时间最多可变化2倍。此外，我们表明，对于具有不对称1,2取代模式的降冰片二烯衍生物，转化率的量子产率高度依赖于溶剂，而对于对称取代的化合物则不是这种情况。使用经典分子动力学（MD）模拟和随时间变化的密度泛函理论（TDDFT）计算，可以进一步合理化光谱观察结果。这些证明了振动和旋转激发对于获得宽带吸收的重要性，这是捕获宽范围太阳光谱的先决条件。

更新日期：2019-03-15

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