Diindenoanthracene Diradicaloids Enable Rational, Incremental Tuning of Their Singlet-Triplet Energy Gaps
Diindenoanthracene Diradicaloids Enable Rational, Incremental Tuning of Their Singlet-Triplet Energy Gaps
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DOI：
10.1016/j.chempr.2020.02.010
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发表时间：
2020-06-11
期刊：
影响因子：
23.5
通讯作者：
Haley, Michael M.
中科院分区：
文献类型：
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作者：
Dressler, Justin J.;Cardenas Valdivia, Abel;Haley, Michael M.
对开壳双自由基的固有电子和磁性特性的基本了解至关重要，以便可以修改这些特性以创建满足工业潜在需求的分子。然而，迄今为止，在双自由基化合物中系统地实现这一目标的尝试很少。在这里，我们提出了一系列基于二茚并[1,2-b:1',2'-g]蒽框架的分子的合成、光谱和计算研究。计算表明，通过改变传递积分项 t ab ，我们能够操纵双自由基特征，从而操纵这一系列分子中的 Delta E-ST。超导量子干涉装置（SQUID）磁力测量的实验测定值表明，我们可以在1.6 kcal mol(-1)的狭窄范围内有效地“调整”五种导数的Delta E-ST。
A fundamental understanding of the inherent electronic and magnetic properties of open-shell diradicaloids is essential so that these properties can be modified to create molecules that meet the potential needs of industry. However, there have been very few attempts to date to systematically accomplish this in diradicaloid compounds. Here, we present the synthetic, spectroscopic, and computational investigation of a series of molecules based on the diindeno[1,2-b:1',2'-g]anthracene framework. Calculations suggest that by altering the transfer integral term, t ab , we are able to manipulate the diradical character and, thus, Delta E-ST within this series of molecules. Experimentally determined values by superconducting quantum interference device (SQUID) magnetometry show that we can effectively "tune" Delta E-ST of the five derivatives within a narrow 1.6 kcal mol(-1) range.