Toward Benzobis(thiadiazole)‐based Diradicaloids

Liu, Yi; Phan, Hoa; Herng, Tun Seng; Gopalakrishna, Tullimilli Y.; Ding, Jun; Wu, Jishan

doi:10.1002/asia.201700732

Cited by 25 publications

(18 citation statements)

References 37 publications

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“…The formation of 2 could be due to the debromination of the porphyrin‐BBT intermediate followed by homocoupling of the as‐generated radicals, considering the intrinsic radical character of BBT. The Sonogashira coupling reaction between 7 and 8 20 was performed under similar conditions, giving dye 3 in a 15% yield. Compounds 1 – 3 are stable materials and can be purified by normal silica gel chromatography.…”

Section: Resultsmentioning

confidence: 99%

“…Compound 3 . To a 50‐ml two‐necked flask containing 20 ml THF, was added compound 7 36 (62 mg, 0.05 mmol) and compound 8 20 (46 mg, 0.1 mmol). The mixture was bubbled with nitrogen for 15 min.…”

Section: Methodsmentioning

confidence: 99%

“…However, the synthesis is tedious and the stability of the final products is limited. We also theoretically and experimentally demonstrated that ethynylene‐bridged benzo[1,2‐c;4,5‐cʹ]bis[1,2,5]thiadiazole (BBT) oligomers could show tunable open‐shell diradical character 20 . BBT has been widely incorporated into many organic conductors and donor‐acceptor type low bandgap polymers due to its strong electron‐accepting capability 21–27 .…”

Section: Introductionmentioning

confidence: 99%

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Benzo[1,2‐c;4,5‐cʹ]bis[1,2,5]thiadiazole‐porphyrin‐based near‐infrared dyes

Liu

Gopalakrishna

et al. 2021

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Benzo[1,2‐c;4,5‐cʹ]bis[1,2,5]thiadiazole (BBT) has intrinsic diradical character and herein it is used to construct organic near‐infrared (NIR) dyes together with the aromatic porphyrin unit. Three BBT‐porphyrin hybrid dyes 1–3 with different linkage modes are synthesized by Pd‐catalyzed Sonogashira cross‐coupling between meso‐ethynylene porphyrin units and monobromo‐/dibromo‐ BBT, or through unexpected homocoupling between the BBT units. They all possess small open‐shell diradical character and display intense NIR absorption in the range of 800–1000 nm. They also exhibit amphoteric redox behavior. BBT‐based diradicaloids are thus good candidates for organic NIR dyes.

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Section: Resultsmentioning

confidence: 99%

Section: Methodsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Benzo[1,2‐c;4,5‐cʹ]bis[1,2,5]thiadiazole‐porphyrin‐based near‐infrared dyes

Liu

Gopalakrishna

et al. 2021

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“…Here, we have used CPDT and its derivatives cyclopentadifuran (CPDF) and cyclopentadiselenophene (CPDS) as donors and benzo[1,2-c; 4,5-c’]bis[1,2,5]thiadiazole (BBT) acceptor to design D−A macrocycles (see Figure 1 D). We chose BBT as an acceptor for its high electron affinity and the fact that it intrinsically behaves as a diradical ( Liu et al., 2017 ). As π-spacers can significantly alter the electronic structure, we insert thiophene between the donor and the acceptor units.…”

Section: Resultsmentioning

confidence: 99%

Donor-Acceptor Conjugated Macrocycles with Polyradical Character and Global Aromaticity

2020

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Summary Polyradical character and global aromaticity are fundamental concepts that govern the rational design of cyclic conjugated macromolecules for optoelectronic applications. Here, we report donor-acceptor (D−A) conjugated macromolecules with and without π-spacer derivatives to tune the antiferromagnetic couplings between the unpaired electrons. The macromolecules without π-spacer have a closed-shell electronic configuration and show global nonaromatic character in the singlet and lowest triplet states. However, the derivatives with π-spacer develop a nearly pure open-shell diradical and a very high polyradical character, not reported for D−A type macromolecules. Furthermore, the π-spacer derivatives display global nonaromaticity in the singlet ground state, but global aromaticity in the lowest triplet state, according to Baird's rule. The absorption spectra of the open-shell macromolecules calculated with time-dependent density functional theory indicate intensive light absorption in the near-infrared region and broadening to 2,500 nm, making these materials suitable for numerous optoelectronic applications.

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“… 75 With the rapid development of organic electronics, BBT-based D-A type molecules have been widely synthesized for organic light-emitting diodes, organic photovoltaics, and biophotonics. 76 , 77 , 78 , 79 Recently, a series of BBT-based NIR-II fluorophores have been successfully exploited for cancer imaging and phototherapy ( Table 1 ). 80 , 81 …”

Section: Nir-ii Organic Small Molecular Fluorophoresmentioning

confidence: 99%

Small Molecular NIR-II Fluorophores for Cancer Phototheranostics

et al. 2021

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Summary Phototheranostics integrates deep-tissue imaging with phototherapy (containing photothermal therapy and photodynamic therapy), holding great promise in early diagnosis and precision treatment of cancers. Recently, second near-infrared (NIR-II) fluorescence imaging exhibits the merits of high accuracy and specificity, as well as real-time detection. Among the NIR-II fluorophores, organic small molecular fluorophores have shown superior properties in the biocompatibility, variable structure, and tunable emission wavelength than the inorganic NIR-II materials. What's more, some small molecular fluorophores also display excellent cytotoxicity when illuminated with the NIR laser. This review summarizes the progress of small molecular NIR-II fluorophores with different central cores for cancer phototheranostics in the past few years, focusing on the molecular structures and phototheranostic performances. Furthermore, challenges and prospects of future development toward clinical translation are discussed.

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Toward Benzobis(thiadiazole)‐based Diradicaloids

Cited by 25 publications

References 37 publications

Benzo[1,2‐c;4,5‐cʹ]bis[1,2,5]thiadiazole‐porphyrin‐based near‐infrared dyes

Benzo[1,2‐c;4,5‐cʹ]bis[1,2,5]thiadiazole‐porphyrin‐based near‐infrared dyes

Donor-Acceptor Conjugated Macrocycles with Polyradical Character and Global Aromaticity

Small Molecular NIR-II Fluorophores for Cancer Phototheranostics

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