Highly efficient organic photocatalysts discovered via a computer-aided-design strategy for visible-light-driven atom transfer radical polymerization

Singh, Varun Kumar; Yu, Changhoon; Badgujar, Sachin; Kim, Young-Mu; Kwon, Yonghwan; Kim, Doyon; Lee, Junhyeok; Akhter, Toheed; Thangavel, Gurunathan; Park, Lee Soon; Lee, Jiseok; Nandajan, Paramjyothi C.; Wannemacher, Reinhold; Milián‐Medina, Begoña; Lüer, Larry; Kim, Kwang S.; Gierschner, Johannes; Kwon, Min Sang

doi:10.1038/s41929-018-0156-8

Cited by 162 publications

(229 citation statements)

References 55 publications

Supporting

Mentioning

228

Contrasting

Order By: Relevance

“…[47] Conversely, for states with very pronounced CT character, B3LYP performs again well, as here the inherent overdelocalization error does not affect the results. [48][49] Using OC-M06HF for the TD part, the spectral positions of AQ2 and NQ2 agree sufficiently well with experiment ( Figure 3); it is noted, however, that the oscillator strengths (and thus, molar extinction coefficients) are systematically overestimated to some degree. Although this is a drawback for quantitative evaluation, the better agreement in the spectral positions is surely more important for practical applications.…”

Section: Td-dft Methods Selection For the Spectral Analysissupporting

confidence: 66%

Combined Spectroscopic and TD‐DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino‐ versus Nitro‐Substituted 2,4‐Diphenylquinolines

et al. 2020

Self Cite

View full text Add to dashboard Cite

A combined spectroscopic and TD‐DFT case study was performed, to identify a robust method to calculate the complex near UV/Vis absorption spectra of various amino‐ vs. nitro‐substituted 2,4‐diphenylquinolines, which vary strongly under neutral and successively acidic conditions. For this, different DFT functionals were tested for geometry optimization and the TD part to calculate the neutral and different protonated species in a fast screening approach, i. e. using single point calculations in an implicit solvent. Offset‐corrected M06HF, hitherto only applied to polymers, was identified as a suitable method to reproduce the absorption spectra in a reasonable fashion for all different substitution pattern and all different protonated species at different pH values; moreover, the method properly predicts the energetic ordering of low‐lying n‐π* and ππ* transitions, which is decisive for the non‐/emissive nature of the different compounds. In all, this might provide a valuable tool for computer‐aided design of related classes of compounds.

show abstract

Section: Td-dft Methods Selection For the Spectral Analysissupporting

confidence: 66%

Combined Spectroscopic and TD‐DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino‐ versus Nitro‐Substituted 2,4‐Diphenylquinolines

et al. 2020

Self Cite

View full text Add to dashboard Cite

show abstract

“…It has been confirmed that a small Δ E ST value, which was usually achieved by HOMO–LUMO separation of PSs, is beneficial for high 1 O 2 generation efficiency. In TBT, the combined acceptor shows stronger electron withdrawing ability than a single acceptor, leading to stronger charge transfer in TBT rather than that in TPT , which is benefit to realize small Δ E ST value . On the other hand, as shown in Figure A, due to the steric effect of BT unit, the dihedral angle between the plane of the donor TPE and the plane of main acceptor TCF in TBT is 78.5°, nearly perpendicular to each other.…”

Section: Resultsmentioning

confidence: 97%

Precise Molecular Engineering of Photosensitizers with Aggregation‐Induced Emission over 800 nm for Photodynamic Therapy

Mao

et al. 2019

Adv Funct Materials

104

View full text Add to dashboard Cite

Owing to efficient singlet oxygen ( 1 O 2 ) generation in aggregate state, photosensitizers (PSs) with aggregation-induced emission (AIE) have attracted much research interests in photodynamic therapy (PDT). In addition to high 1 O 2 generation efficiency, strong molar absorption in longwavelength range and near-infrared (NIR) emission are also highly desirable, but difficult to achieve for AIE PSs since the twisted structures in AIE moieties usually lead to absorption and emission in short-wavelength range. In this contribution, through acceptor engineering, a new AIE PS of TBT is designed to show aggregation-induced NIR emission centered at 810 nm, broad absorption in the range between 300 and 700 nm with a large molar absorption coefficient and a high 1 O 2 generation efficiency under white light irradiation. Further, donor engineering by attaching two branched flexible chains to TBT yielded TBTC8, which circumvented the strong intermolecular interactions of TBT in nanoparticles (NPs), yielding TBTC8 NPs with optimized overall performance in 1 O 2 generation, absorption, and emission. Subsequent PDT results in both in vitro and in vivo studies indicate that TBTC8 NPs are promising candidates in practical application.The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/adfm.201901791.(ROS) to kill cancer cells under light irradiation, has drawn widespread research interests owing to its good spatiotemporal precision, precise controllability, and noninvasiveness, etc. [1] Among which, the process that using emissive PSs as the key agents to find out the tumor site first and then realize PDT has been recognized as cost-effective and time-saving due to the integration of both diagnosis and treatment in one molecule. [2] To achieve effective PDT, smart design of PSs is of essential significance. Ideal properties of PSs include efficient 1 O 2 generation ability for cancer cell ablation, near-infrared (NIR) emission for imaging, strong absorption in long wavelength for easy excitation and good penetration depth, negligible dark toxicity for minimal side effects, and good photostability for continuous light irradiation. [3] Boron-dipyrromethene (BODIPY) derivatives, [4] metal complexes, [5] cyanine derivatives, [6] and porphyrin or chlorin derivatives, [7] are some typical traditional PSs. Heavy atoms are usually used to improve the 1 O 2 generation efficiency of BODIPY derivatives and metal complexes, which usually exhibit nontrivial dark toxicity with weak fluorescence. [4,5] Cyanine-type PSs are famous for their large absorbance in long-wavelength range with bright NIR emission over 800 nm. However, their poor 1 O 2 production capability and low photostability limited their practical application. [6] Porphyrin and chlorin derivatives usually show good 1 O 2 generation, but their light-absorbing capacity in long-wavelength range is generally rather poor, and their emission peaks are relatively blue as compared to those of cyanine-type PSs. [7] Several ...

show abstract

“…Notably, the RISC process from T 1 to S 1 states becomes increasingly a competitive pathway that will impede the population of triplet excitons when the energy difference Δ E T1→S1 is smaller (<0.37 eV), which caused the well‐known TADF phenomenon . Obviously, the RISC process is harmful to the RTP in organic molecules, but it facilitates the utilization of triplet excitons.…”

Section: General Principle In Organic Phosphorescencementioning

confidence: 99%

“…achieved ultralong‐lived organic RTP in π‐orbital‐providing 1,3,5‐triazines derivatives with a lifetime of 1.35 s, but its absolute quantum efficiency is only ≈1.25% . Interestingly, the thermally‐activated delayed fluorescence (TADF), known as an emission triggered through a reverse intersystem crossing (RISC) process from the lowest triplet to singlet excited states, was also observed in some RTP molecules . In this case, the RTP phenomenon becomes more difficult to understand owing to the RISC deactivation process of the triplet excitons.…”

Section: Introductionmentioning

confidence: 99%

Room‐Temperature Phosphorescence in Metal‐Free Organic Materials

et al. 2019

Annalen der Physik

View full text Add to dashboard Cite

Purely organic materials with room-temperature phosphorescence (RTP) have attracted a growing interest for their potential applications in biological imaging, digital encryption, optoelectronic devices, and so on. To date, many strategies have succeeded in designing efficient organic RTP materials by overcoming the spin-forbidden transition between singlet and triplet states. However, the underlying mechanisms of RTP still remain ambiguous. Such spin prohibition in phosphorescence are clarified, herein, from the perspective of perturbation theory, helping to understand the intrinsic relationship among various phosphorescence parameters, like phosphorescence efficiency, lifetime, intersystem crossing rate, as well as radiative and nonradiative rates. Taking into consideration the recent progress in organic RTP materials, these factors are further illustrated by a selection of the most relevant molecules. In addition, some novel RTP phenomena are also reviewed, thus providing an excellent guideline to constructing efficient RTP materials.

show abstract

Highly efficient organic photocatalysts discovered via a computer-aided-design strategy for visible-light-driven atom transfer radical polymerization

Cited by 162 publications

References 55 publications

Combined Spectroscopic and TD‐DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino‐ versus Nitro‐Substituted 2,4‐Diphenylquinolines

Combined Spectroscopic and TD‐DFT Analysis to Elucidate Substituent and Acidochromic Effects in Organic Dyes: A Case Study on Amino‐ versus Nitro‐Substituted 2,4‐Diphenylquinolines

Precise Molecular Engineering of Photosensitizers with Aggregation‐Induced Emission over 800 nm for Photodynamic Therapy

Room‐Temperature Phosphorescence in Metal‐Free Organic Materials

Contact Info

Product

Resources

About