Symmetry-Directed Control of Electronic Coupling for Singlet Fission in Covalent Bis鈥揂cene Dimers

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• 作者：Niels H. Damrauer ; Jamie L. Snyder
• 刊名：The Journal of Physical Chemistry Letters
• 出版年：2015
• 出版时间：November 19, 2015
• 年：2015
• 卷：6
• 期：22
• 页码：4456-4462
• 全文大小：401K
• ISSN：1948-7185

文摘

While singlet fission (SF) has developed in recent years within material settings, much less is known about its control in covalent dimers. Such platforms are of fundamental importance and may also find practical use in next-generation dye-sensitized solar cell applications or for seeding SF at interfaces following exciton transport. Here, facile theoretical tools based on Boys localization methods are used to predict diabatic coupling for SF via determination of one-electron orbital coupling matrix elements. The results expose important design rules that are rooted in point group symmetry. For C_s-symmetric dimers, pathways for SF that are mediated by virtual charge transfer excited states destructively interfere with negative impact on the magnitude of diabatic coupling for SF. When dimers have C₂ symmetry, constructive interference is enabled for certain readily achievable interchromophore orientations. Three sets of dimers exploiting these ideas are explored: a bis鈥搕etracene pair and two sets of aza-substituted tetracene dimers. Remarkable control is shown. In one aza-substituted set, symmetry has no impact on SF reaction thermodynamics but leads to a 16-fold manipulation in SF diabatic coupling. This translates to a difference of nearly 300 in k_SF with the faster of the two dimers (C₂) being predicted to undergo the process on a nearly ultrafast 1.5 ps time scale.