Derivation of saddle shaped cyclooctatetrathiophene: increasing conjugation and fabricating pentamer

Wang, Yong; De-wen, Gao; Shi, Jianwu; Kan, Yuhe; Song, Jinsheng; Li, Chunli; Wang, Hua

doi:10.1016/j.tet.2013.12.002

Cited by 44 publications

(36 citation statements)

References 34 publications

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“…Te tra [2,3]thienylene tetracarboxylic acid tetraethyl ester 2 was synthesized from 4-bromo-2-thiophene carboxylic acid as described in the literature. [23] Four-fold hydrolysis of 2 under aqueous basic conditions gave the corresponding tetracarboxylic acid 1.W ea lso attempted to prepare 1 from tetrabromo derivative 3 [24] by four-fold lithiation followed by the reaction with CO 2 .H owever,t his attempt was unsuccessful due to the incomplete reaction and the difficulty of purification from the mixture of 1 and partly carboxylated byproducts.…”

Section: Resultsmentioning

confidence: 99%

Jumping Crystal of a Hydrogen‐Bonded Organic Framework Induced by the Collective Molecular Motion of a Twisted π System

2019

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There is alimited number of reports on mechanically responsive molecular crystals,i ncluding thermo-responsive and light-responsive crystals.Rigid ordered molecular crystals with aclose-packing structure are less able to accept distortion, which hampers the development of such molecular crystals. The thermosalient effect, or "crystal jumping", refers to athermo-responsive system that converts heat into mechanical force by thermally induced phase transition. While they have recently attracted attention as potential highly efficient molecular actuators,less than two dozens of thermosalient molecular crystals have been reported to date,a nd the design of such molecules as well as how they assemble to express at hermosalient effect are unknown. Herein, we demonstrate how the cooperative molecular motion of twisted p units could serve to develop at hermo-responsive jumping molecular crystal with ah ydrogen-bonded organic framework (HOF) of tetra-[2,3]thienylene tetracarboxylic acid (1). The cooperative change in the molecular structure triggered by the desolvation of THF in the channel of the HOF structure induced not only ac hangei nt he structure of HOF but also mechanical force. Hydrogen bonding interactions contributed significant thermal stability to maintain the HOF assembly even with ad ynamic structural change.

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Section: Resultsmentioning

confidence: 99%

Jumping Crystal of a Hydrogen‐Bonded Organic Framework Induced by the Collective Molecular Motion of a Twisted π System

2019

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“…另一方面, 通过 n-BuLi 夺 3TMS-COTh 噻吩环上 α-位质子, 所形成的碳负离子与 2-异丙氧基-4,4,5,5-四甲基-1,3,2-二氧环戊硼烷反应制备环八四噻吩的硼酸酯 (B-3TMS-COTh) [7a] , 其后与 1,3,6,8-四溴芘通过 Suzuki 偶联反应合成目标化合物 12TMS-4COTh-Py. 化合物 4TMS-COTh 通过 N-溴代丁二酰亚胺(NBS)在乙酸中直接四溴代, 四溴代化合物 4Br-COTh [5] 与 1-芘硼酸通过 Suzuki 偶联反应获得目标化合物 4Py-COTh. 1.2 化合物的光谱性质 1.2.1 吸收光谱图 1 给出了三个目标化合物的紫外可见吸收光谱, 包含 280～300 nm 的环八四噻吩(COTh)骨架的吸收 [5] 与 320～420 nm 范围的芘基与相连噻吩环之间的共轭吸收; 与 Py-COTh 在 357 nm 处的吸收峰相比, 芘基数量的增加, 造成了 4Py-COTh 的长波长吸收峰的强度大大增加, 但其峰位(363 nm)只红移了 6 nm, 说明多个芘基的引入对整个分子的共轭效应的贡献有限不大.…”

Section: 结果与讨论unclassified

“…化合物 4TMS-COTh 通过 N-溴代丁二酰亚胺(NBS)在乙酸中直接四溴代, 四溴代化合物 4Br-COTh [5] 与 1-芘硼酸通过 Suzuki 偶联反应获得目标化合物 4Py-COTh. 1.2 化合物的光谱性质 1.2.1 吸收光谱图 1 给出了三个目标化合物的紫外可见吸收光谱, 包含 280～300 nm 的环八四噻吩(COTh)骨架的吸收 [5] 与 320～420 nm 范围的芘基与相连噻吩环之间的共轭吸收; 与 Py-COTh 在 357 nm 处的吸收峰相比, 芘基数量的增加, 造成了 4Py-COTh 的长波长吸收峰的强度大大增加, 但其峰位(363 nm)只红移了 6 nm, 说明多个芘基的引入对整个分子的共轭效应的贡献有限不大. 4Py-COTh 的长波吸收峰强度相当于四个 Py-COTh 的长波吸收峰强度的加和, 这一现象是由环八四噻吩结构单元自身的交叉共轭的特点决定的 [5] .…”

Section: 结果与讨论unclassified

“…4Py-COTh 的长波吸收峰强度相当于四个 Py-COTh 的长波吸收峰强度的加和, 这一现象是由环八四噻吩结构单元自身的交叉共轭的特点决定的 [5] . 然而 12TMS-4CO-Th-Py 表现出非常显著的吸收峰位的红移, 最大吸收峰 [5] . 这就造成了一方面分子自身的共轭性较好, 另一方面激发态下可能形成分子间的类似激基缔合物的相互作用, 从而产生长波长的发射.…”

Section: 结果与讨论unclassified

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Synthesis of Pyrene-Cyclooctatetrathiophene Derivatives and Their Behaviors of Photoluminescence

Yang¹,

Xu²,

Wang³

2020

Chin. J. Org. Chem.

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Cyclooctatetrathiophene (COTh) is a saddle-typed molecule with the interesting property of aggregation induced emission (AIE) discovered recently. In this paper, pyrene was introduced to the framework of COTh as a luminescent group. Three pyrene-COTh derivatives, mono-pyrene substituted COTh (Py-COTh), tetra-pyrene substituted COTh (4Py-COTh) and tetra(tri(trimethylsilyl)cyclooctatetrathiophenyl)pyrene (12TMS-4COTh-Py) were designed and synthesized. Their absorption spectra, fluorescene emission behaviors in solution, rigid state (77 K) and the aggregation state were explored. On the one hand, with increasing pyrene group to the framework of COTh, the molecular conjugation of pyrene-COTh derivatives, Py-COTh and 4Py-COTh changed slightly, but their emission intensity increased heavily with large red shift in both dilute solution and aggregation state. On the other hand, with the increase of COTh group to the framework of pyrene, the molecular conjugation of pyrene-COTh derivatives, Py-COTh and 12TMS-4COTh-Py changed significantly, and their emission intensity increased remarkably with large red shift in dilute solution. The relationship between the photophysical property and molecular structure is remarkably exhibited in our case.

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“…Herein, we synthesized a new HTM named 2,2′,7,7′‐tetrakis(N, N‐di‐p‐methoxyphenyl‐aniline)‐α, β‐cycloocta[1,2‐b:4,3‐b′:5,6‐b″8,7‐b″′]tetrathiophenyl (α, β‐COTh‐Ph‐OMeTAD) with a HOMO/LUMO energy of −5.30/−2.91 eV as shown in Figure a, which containing a cyclooctatetrathiophene (COTh), a saddle‐shaped motif as core, and four diphenylamine units as arms. Comparing with spiro‐OMeTAD as shown in Figure b, the new molecule may have following advantages: COTh is a more flexible saddle shaped structure than that rigid spiro one in spiro‐OMeTAD, which makes the confirmation of α, β‐COTh‐Ph‐OMeTAD to fit perovskite layer better, leading to better interaction with perovskite.…”

Section: Introductionmentioning

confidence: 99%

A Bifunctional Saddle‐Shaped Small Molecule as a Dopant‐Free Hole Transporting Material and Interfacial Layer for Efficient and Stable Perovskite Solar Cells

et al. 2019

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Herein, a new bifunctional saddle-shaped organic small molecule named 2,2 0 ,7,7 0 -tetrakis(N, N-di-p-methoxyphenyl-aniline)-α, β-cycloocta[1,2-b:4,3-b 0 :5,6b 0 :8,7-b 000 ]tetrathiophenyl (α, β-COTh-Ph-OMeTAD) is synthesized. When compared with spiro-OMeTAD, a star hole transporting material (HTM) for highly efficient perovskite solar cells, the new material has a deeper highest occupied molecular orbital (HOMO) energy level of À5.30 eV, and a higher hole mobility of 2.88 Â 10 À4 cm 2 V À1 s À1 . With dopant-free α, β-COTh-Ph-OMeTAD as a HTM and an interfacial layer combinined with chlorobenzene (CB) as the anti-solvent, mesoporous perovskite solar cells (PSCs) are fabricated, which exhibit a power conversion efficiency (PCE) of 17.22% under AM 1.5 conditions, which is a little higher than that of devices based-on doped spiro-OMeTAD under the same conditions, which is 16.83%. Notably, the PSCs devices with dopant-free α, β-COTh-Ph-OMeTAD as both the HTM and interfacial layer show better stability, and after being stored in dark and dry air without encapsulation for nearly 800 h, the PCE can still be maintained at 86% of the maximum. This opens a new avenue for efficient and stable PSCs by exploring new dopant-free materials as alternatives to spiro-OMeTAD.

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Derivation of saddle shaped cyclooctatetrathiophene: increasing conjugation and fabricating pentamer

Cited by 44 publications

References 34 publications

Jumping Crystal of a Hydrogen‐Bonded Organic Framework Induced by the Collective Molecular Motion of a Twisted π System

Jumping Crystal of a Hydrogen‐Bonded Organic Framework Induced by the Collective Molecular Motion of a Twisted π System

Synthesis of Pyrene-Cyclooctatetrathiophene Derivatives and Their Behaviors of Photoluminescence

A Bifunctional Saddle‐Shaped Small Molecule as a Dopant‐Free Hole Transporting Material and Interfacial Layer for Efficient and Stable Perovskite Solar Cells

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