{"title":"Two-photon absorption of BODIPY, BIDIPY, GADIPY, and SBDIPY†","authors":"Ismael A. Elayan, Mingmin Zhou and Alex Brown","doi":"10.1039/D4CP03915G","DOIUrl":null,"url":null,"abstract":"<p >Substituted boron-dipyrromethene compounds (BODIPYs) have gained significant attention due to their tunable photophysical properties, including two-photon absorption (2PA), a nonlinear optical process where two photons are absorbed simultaneously. The tuning of BODIPY's photophysical properties has recently led to the synthesis of pnictogen-containing derivatives, such as SBDIPY and BIDIPY, where boron is replaced by antimony (Sb) or bismuth (Bi), respectively, as well as other analogues like GADIPY, which contain gallium (Ga). This study presents a computational investigation into their 2PA properties, exploring the impact of various substitutions across these systems. The 2PA cross-sections (<em>σ</em><small><sup>2PA</sup></small>), electronic excitation energies (Δ<em>E</em>), and dipole moments (<em>μ</em><small><sub>00</sub></small>, <em>μ</em><small><sub>11</sub></small>, <em>μ</em><small><sub>01</sub></small>, Δ<em>μ</em>) were computed for 18 DIPY chromophores in the gas-phase with time-dependent density-functional theory (TD-DFT) using several functionals (CAM-B3LYP, ωB97X, M06-2X, M11, and MN15), and then compared to second-order approximate coupled-cluster with the resolution-of-identity approximation (RI-CC2) results. The computed mean absolute errors were small, with the MN15, CAM-B3LYP, and M06-2X functionals being among the best-performing for the properties analyzed. In general, for the parent (unsubstituted) compounds, replacing the core atom in DIPY chromophores results in negligible changes to their <em>σ</em><small><sup>2PA</sup></small>. However, extending the conjugation through the addition of phenyl substituents significantly increases <em>σ</em><small><sup>2PA</sup></small> values, and the nature of the core atom impacts the magnitude of this enhancement.</p>","PeriodicalId":99,"journal":{"name":"Physical Chemistry Chemical Physics","volume":" 7","pages":" 3873-3884"},"PeriodicalIF":2.9000,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/cp/d4cp03915g?page=search","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Physical Chemistry Chemical Physics","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/cp/d4cp03915g","RegionNum":3,"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
Substituted boron-dipyrromethene compounds (BODIPYs) have gained significant attention due to their tunable photophysical properties, including two-photon absorption (2PA), a nonlinear optical process where two photons are absorbed simultaneously. The tuning of BODIPY's photophysical properties has recently led to the synthesis of pnictogen-containing derivatives, such as SBDIPY and BIDIPY, where boron is replaced by antimony (Sb) or bismuth (Bi), respectively, as well as other analogues like GADIPY, which contain gallium (Ga). This study presents a computational investigation into their 2PA properties, exploring the impact of various substitutions across these systems. The 2PA cross-sections (σ2PA), electronic excitation energies (ΔE), and dipole moments (μ00, μ11, μ01, Δμ) were computed for 18 DIPY chromophores in the gas-phase with time-dependent density-functional theory (TD-DFT) using several functionals (CAM-B3LYP, ωB97X, M06-2X, M11, and MN15), and then compared to second-order approximate coupled-cluster with the resolution-of-identity approximation (RI-CC2) results. The computed mean absolute errors were small, with the MN15, CAM-B3LYP, and M06-2X functionals being among the best-performing for the properties analyzed. In general, for the parent (unsubstituted) compounds, replacing the core atom in DIPY chromophores results in negligible changes to their σ2PA. However, extending the conjugation through the addition of phenyl substituents significantly increases σ2PA values, and the nature of the core atom impacts the magnitude of this enhancement.
期刊介绍:
Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions.
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