Brandon K. Rugg, Angana De, Sarath Santhakumar, Qiushi Ma, Brian Fluegel, Karl J. Thorley, John E. Anthony, Libai Huang, Justin C. Johnson
{"title":"Distinct Mechanisms of Triplet Pair Decay in Amorphous and Crystalline Heteroacene Thin Films","authors":"Brandon K. Rugg, Angana De, Sarath Santhakumar, Qiushi Ma, Brian Fluegel, Karl J. Thorley, John E. Anthony, Libai Huang, Justin C. Johnson","doi":"10.1002/cptc.202400224","DOIUrl":null,"url":null,"abstract":"<p>Triplet pairs (TT) in crystalline molecular semiconductors have unique spin properties of interest for quantum information or enhancing solar photoconversion. The population and diffusion dynamics of TT have been the subject of recent studies, both in covalent dimers and in crystalline systems. Here, we monitor the triplet population in neat polycrystalline and amorphous films of a heteroacene with known TT spectral properties and tunable spin polarization depending on the intermolecular geometry. Transient measurements reveal an anomalous power dependence in polycrystalline films that we attribute to the fast diffusion and interaction of dissociated triplet pairs confined to one-dimensional stacks of strongly coupled molecules. The nongeminate triplet interaction after dephasing facilitates conversion to the triplet <sup>3</sup>TT and eventually T<sub>1</sub>+S<sub>0</sub>. Amorphous films have no power dependence and proceed directly from <sup>1</sup>TT to <sup>3</sup>TT and subsequently T<sub>1</sub>+S<sub>0</sub> via state mixing facilitated by nonparallel geometries and weak exchange coupling.</p>","PeriodicalId":10108,"journal":{"name":"ChemPhotoChem","volume":"9 3","pages":""},"PeriodicalIF":3.0000,"publicationDate":"2024-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ChemPhotoChem","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/cptc.202400224","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
引用次数: 0
Abstract
Triplet pairs (TT) in crystalline molecular semiconductors have unique spin properties of interest for quantum information or enhancing solar photoconversion. The population and diffusion dynamics of TT have been the subject of recent studies, both in covalent dimers and in crystalline systems. Here, we monitor the triplet population in neat polycrystalline and amorphous films of a heteroacene with known TT spectral properties and tunable spin polarization depending on the intermolecular geometry. Transient measurements reveal an anomalous power dependence in polycrystalline films that we attribute to the fast diffusion and interaction of dissociated triplet pairs confined to one-dimensional stacks of strongly coupled molecules. The nongeminate triplet interaction after dephasing facilitates conversion to the triplet 3TT and eventually T1+S0. Amorphous films have no power dependence and proceed directly from 1TT to 3TT and subsequently T1+S0 via state mixing facilitated by nonparallel geometries and weak exchange coupling.
ChemPhotoChemChemistry-Physical and Theoretical Chemistry
CiteScore
5.80
自引率
5.40%
发文量
165
期刊介绍:
Light plays a crucial role in natural processes and leads to exciting phenomena in molecules and materials. ChemPhotoChem welcomes exceptional international research in the entire scope of pure and applied photochemistry, photobiology, and photophysics. Our thorough editorial practices aid us in publishing authoritative research fast. We support the photochemistry community to be a leading light in science.
We understand the huge pressures the scientific community is facing every day and we want to support you. Chemistry Europe is an association of 16 chemical societies from 15 European countries. Run by chemists, for chemists—we evaluate, publish, disseminate, and amplify the scientific excellence of chemistry researchers from around the globe.