Polymorphism Controlled Singlet Fission in TIPS-Anthracene: Role of Stacking Orientation

IF 3.2 3区 化学 Q2 CHEMISTRY, PHYSICAL
Kalishankar Bhattacharyya, Ayan Datta*
{"title":"Polymorphism Controlled Singlet Fission in TIPS-Anthracene: Role of Stacking Orientation","authors":"Kalishankar Bhattacharyya,&nbsp;Ayan Datta*","doi":"10.1021/acs.jpcc.6b10075","DOIUrl":null,"url":null,"abstract":"<p >Generation of multiple triplet excitons from one singlet exciton (singlet fission, SF) has been reported in several organic molecules recently. The overall SF yield in such molecular materials, however, is controlled by polymorphism in organic semiconductors through noncovalent interactions like van der Waals and weak electrostatic interactions. In this article, we demonstrate how SF is strongly perturbed by even small variations in molecular packing for polymorphic crystals of triisopropylsilyethnyl-anthracene derivatives, TIPS-Ant (<b>PI</b> and <b>PII</b>). Based on quantum chemical calculations, SF dynamics have been computed for both <b>PI</b> and <b>PII</b> polymorphs. <b>PI</b> and <b>PII</b> differ in their intermolecular π···π stacking patterns, which eventually control their electronic properties. Using the incoherent hopping model for the crystals, we computed SF rate through the Marcus electron transfer theory. For both <b>PI</b> and <b>PII</b>, the direct two-electron pathway predominates over the charge-transfer (CT) mediated mechanism. <b>PII</b> has higher triplet yield (~196%) compared to <b>PI</b> (~178%). Both time-dependent DFT as well as Weller equation reveal that the charge transfer (CT) state is a high energy state, and hence, CT mediated SF barely influences triplet yield. Interplay of the local excitation (LE), multiple excitation (ME), and correlated triplet (T<sub>1</sub>T<sub>1</sub>) energy levels controlled the overall exciton dynamics/diffusion in TIPS-Ant polymorphs. Polymorphism is shown to be a key factor for the rational design of optimal SF in polyaromatic hydrocarbons (PAH).</p>","PeriodicalId":61,"journal":{"name":"The Journal of Physical Chemistry C","volume":"121 3","pages":"1412–1420"},"PeriodicalIF":3.2000,"publicationDate":"2017-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1021/acs.jpcc.6b10075","citationCount":"50","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry C","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jpcc.6b10075","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 50

Abstract

Generation of multiple triplet excitons from one singlet exciton (singlet fission, SF) has been reported in several organic molecules recently. The overall SF yield in such molecular materials, however, is controlled by polymorphism in organic semiconductors through noncovalent interactions like van der Waals and weak electrostatic interactions. In this article, we demonstrate how SF is strongly perturbed by even small variations in molecular packing for polymorphic crystals of triisopropylsilyethnyl-anthracene derivatives, TIPS-Ant (PI and PII). Based on quantum chemical calculations, SF dynamics have been computed for both PI and PII polymorphs. PI and PII differ in their intermolecular π···π stacking patterns, which eventually control their electronic properties. Using the incoherent hopping model for the crystals, we computed SF rate through the Marcus electron transfer theory. For both PI and PII, the direct two-electron pathway predominates over the charge-transfer (CT) mediated mechanism. PII has higher triplet yield (~196%) compared to PI (~178%). Both time-dependent DFT as well as Weller equation reveal that the charge transfer (CT) state is a high energy state, and hence, CT mediated SF barely influences triplet yield. Interplay of the local excitation (LE), multiple excitation (ME), and correlated triplet (T1T1) energy levels controlled the overall exciton dynamics/diffusion in TIPS-Ant polymorphs. Polymorphism is shown to be a key factor for the rational design of optimal SF in polyaromatic hydrocarbons (PAH).

Abstract Image

tips -蒽中多态控制单线态裂变:堆叠取向的作用
一个单线态激子产生多个三重态激子(单线态裂变,SF)最近在一些有机分子中被报道。然而,这种分子材料的整体SF产率是由有机半导体中的多态性控制的,通过范德华和弱静电相互作用等非共价相互作用。在这篇文章中,我们展示了三异丙基硅乙基蒽衍生物TIPS-Ant (PI和PII)的多晶晶体的分子堆积的微小变化如何强烈地扰动SF。基于量子化学计算,计算了PI和PII多态的SF动力学。PI和PII的分子间π··π堆叠模式不同,这最终控制了它们的电子性质。利用晶体的非相干跳变模型,利用Marcus电子转移理论计算了SF速率。对于PI和PII,直接的双电子途径优于电荷转移(CT)介导的机制。PII比PI(~178%)具有更高的三重态产率(~196%)。随时间变化的DFT和Weller方程都表明电荷转移(CT)态是一个高能态,因此,CT介导的SF几乎不影响三重态产率。局部激发(LE)、多重激发(ME)和相关三重态(T1T1)能级的相互作用控制了TIPS-Ant多晶态的整体激子动力学/扩散。多态性是设计多环芳烃(PAH)最优顺位结构的关键因素。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
The Journal of Physical Chemistry C
The Journal of Physical Chemistry C 化学-材料科学:综合
CiteScore
6.50
自引率
8.10%
发文量
2047
审稿时长
1.8 months
期刊介绍: The Journal of Physical Chemistry A/B/C is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信