N-hexyl-2,5-di(2-thienyl)pyrrole

• 分子结构分类: 有机化合物 - 有机杂环化合物 - 吡咯
• 英文名称: N-hexyl-2,5-di(2-thienyl)pyrrole
• 英文别名: 1-Hexyl-2,5-dithiophen-2-ylpyrrole
• 化学式: C₁₈H₂₁NS₂
• 分子量: 315.503
• InChiKey: HNBTUOHUAAHMJU-UHFFFAOYSA-N

计算性质

• 辛醇/水分配系数(LogP)：
  5.7
• 重原子数：
  21
• 可旋转键数：
  7
• 环数：
  3.0
• sp3杂化的碳原子比例：
  0.33
• 拓扑面积：
  61.4
• 氢给体数：
  0
• 氢受体数：
  2

反应信息

• 作为反应物：
  描述：

  N-hexyl-2,5-di(2-thienyl)pyrrole 在 正丁基锂 、 四甲基乙二胺 、 碘 作用下， 以 四氢呋喃 、 正己烷 为溶剂， 反应 25.0h， 以89%的产率得到N-hexyl-2,5-bis(5-iodo-2-thienyl)pyrrole
  参考文献：
  名称：

  Synthesis and structural, electronic, optical and FET properties of thiophene–pyrrole mixed hexamers end-capped with phenyl and pentafluorophenyl groups

  摘要：

  新合成了以两个苯基、两个五氟苯基以及苯基和五氟苯基为端盖的δ-连接噻吩吡咯混合六聚体3aâ5a，并研究了它们的结构、电子、光学和场效应晶体管特性。通过 X 射线晶体学和理论计算进行的结构分析表明，由于吡咯单元的己基与相邻的噻吩分子之间存在立体排斥，低聚物链的Ï-系统是扭曲的。从吸收最大值和氧化还原电位的比较来看，苯基和五氟苯基单元的端封并不影响噻吩吡咯六聚物的 HOMOâLUMO 间隙，而多个氟取代基在电负性氟原子的感应作用下会略微降低 HOMO 和 LUMO 水平。虽然具有人字形填料结构的二苯基衍生物 3a 不能用作场效应晶体管器件的活性层，但在加热时却观察到了独特的晶体-晶体相变，颜色从黄色变为红色。与 3a 的人字形堆积结构不同，不对称的苯基五氟苯基衍生物 5a 显示出部分Ï-堆积结构，这很可能是由于偶极与偶极之间的相互作用。5a 的Ï-堆积结构使其在单晶场效应晶体管器件中具有 4.1 Ã 10â2 cm2 Vâ1sâ1 的良好空穴迁移率。

  DOI：

  10.1039/c1jm12966j
• 作为产物：
  描述：

  1,4-双(2-噻吩基)-1,4-丁二酮 、 正己胺 在 丙酸 作用下， 以 甲苯 为溶剂， 反应 16.0h， 生成 N-hexyl-2,5-di(2-thienyl)pyrrole
  参考文献：
  名称：

  Selective bromination of 2,5-bis(2-thienyl)pyrroles and solid-state polymerization through the β-carbon of pyrrole

  摘要：

  通过β-C的吡咯环团固态聚合(SSP)，得到β,β'-二溴-2,5-双(2-噻吩基)吡咯环团的溴掺杂共轭聚合物。

  DOI：

  10.1039/c4ra01993h

文献信息

• Biradical Character of Linear π-Conjugated Oligomer Dications Composed of Thiophene, Pyrrole, and Methylthio End-Capping Units
  作者：Tohru Nishinaga、Masaki Tateno、Mika Fujii、Wataru Fujita、Masayoshi Takase、Masahiko Iyoda

  DOI：10.1021/ol101997w

  日期：2010.12.3

  calculations and UV−vis−NIR, ESR, and SQUID measurements revealed that the ground-state electronic structure of a linear π-conjugated oligomer dication composed of two pyrrole and six or seven thiophene rings and methylthio end-capping units is dominated by a singlet biradical character.

  结合DFT计算和UV-vis-NIR，ESR和SQUID测量表明，由两个吡咯和六个或七个噻吩环和甲硫基封端单元组成的线性π-共轭低聚物基体的电子结构单重双自由基字符。
• Selective bromination of 2,5-bis(2-thienyl)pyrroles and solid-state polymerization through the β-carbon of pyrrole
  作者：Palas Baran Pati、Sanjio S. Zade

  DOI：10.1039/c4ra01993h

  日期：——

  Solid state polymerization (SSP) through β-C of pyrrole of the β,β′-dibrominated 2,5-bis(2-thienyl)pyrrole moiety to afford the bromine doped conjugated polymer.

  通过β-C的吡咯环团固态聚合(SSP)，得到β,β'-二溴-2,5-双(2-噻吩基)吡咯环团的溴掺杂共轭聚合物。
• Molecular and Electronic Structures of Heteroaromatic Oligomers:  Model Compounds of Polymers with Quantum-Well Structures
  作者：Carlos Alemán、Victor M. Domingo、Lluís Fajarí、Luis Juliá、Alfred Karpfen

  DOI：10.1021/jo971357x

  日期：1998.2.1

  Conformational preferences of 2,2'-bithiophene, 2-(2-thienlyl)pyrrole, and N-methyl-2-(2-thienyl)pyrrole have been investigated by means of computational methods. Calculations were performed at the ab initio HF/6-31G(d) and MP2/6-31G(d) levels and, additionally, with the density functional B3-LYP/6-31G(d), The results indicate that 2-(2-thienyl)pyrrole behaves similarly to the 2,2'-bithiophene. Thus, two minimum energy conformations were found for each compound, which correspond to anti-gauche and syn-gauche. Such minima are separated by barriers of about 1.7 and 1.3 kcal/mol at the HF and MP2 levels. On the contrary, the preferences found for N-methyl-2-(2-thienyl)pyrrole were different, giving an almost negligible energy barrier between the two minimum energy conformations. Furthermore, at the MP2 level the anti-gauche and syn-gauche minimum energy conformations present an inter-ring-dihedral of 135 degrees and 68 degrees, respectively, displaying deviations greater than those found in 2,2'-bithiophene and 2-(2-thienyl)pyrrole. The conformational analysis was extended to the tricyclic compound N-methyl-2,5-di(2-thienyl)pyrrole. For this molecule, a contour map of the conformational energy as a function of the inter-ring dihedral angles was computed at the HF/6-31G(d) level. Minimum energy conformations were subsequently computed at the same level of theory. Results were in agreement with those obtained for the bicyclic compound N-methyl-2-(2-thienyl)pyrrole. Thus, the inter-ring dihedral angles of the minimum energy conformations present a large distortion with respect to the planarity, and such minimum energy conformations are separated by almost negligible energy barriers. Finally, N-hexyl-2,5-di(2-thienyl)pyrrole radical cation was observed by EPR spectroscopy. This is the first time that a mixed trimer of thiophene and pyrrole is oxidized to its radical cation and detected by means of EPR spectroscopy. The spectrum seems to be symmetric, which is accounted for by a fast interconversion between conformers. This supports the small energy barrier calculated between minima for the bicyclic and tricyclic compounds. Overall, the results presented in this work indicate that N-methylpyrrole rings are able to induce large rotational deffects in [...-(pyrrole)(n)-(thiophene)(n)-...] block copolymers.
• Panchromatic small molecules for UV-Vis-NIR photodetectors with high detectivity
  作者：Ji Qi、Liang Ni、Dezhi Yang、Xiaokang Zhou、Wenqiang Qiao、Mao Li、Dongge Ma、Zhi Yuan Wang

  DOI：10.1039/c3tc32271h

  日期：——

  Two donor–acceptor–donor (D–A–D) type low-bandgap small molecules, M1 and M2, with bis(2-thienyl)-N-alkylpyrrole (TPT) as the donor and thieno[3,4-b]thiadiazole (TT) as the acceptor were designed and synthesized. The absorption, transmission, electrochemical, thermal and film properties were studied. The compounds showed panchromatic absorption in the spectral range of 300–1000 nm. Moreover, they also exhibited semi-transparent property in the visible region (400–700 nm). Small molecule photodetectors (SMPDs) based on M1 and M2 were fabricated and studied. For the SMPD with BCP as the hole blocking layer (HBL), a detectivity of 5.0 × 1011 Jones at 800 nm at −0.1 V was obtained, which is among the highest detectivities reported for NIR SMPDs. With a sufficiently thin silver electrode, visibly transparent PDs with an average transmittance of 45% in the visible region were obtained for the first time. The transparent PDs exhibited fairly constant and high detectivity between 1011 and 1012 Jones over a broad spectral range of 300–900 nm. In addition, side chains of the compounds exhibited a great influence on the device performance, which could be assigned to their film absorption coefficient, molecular packing and active layer morphology.

  设计并合成了以双（2-噻吩基）-N-烷基吡咯（TPT）为供体、噻吩并[3,4-b]噻二唑（TT）为受体的两种供体-受体-供体（D-A-D）型低带隙小分子 M1 和 M2。研究了这些化合物的吸收、透射、电化学、热和薄膜特性。这些化合物在 300-1000 纳米的光谱范围内具有全色吸收。此外，它们还在可见光区域（400-700 纳米）表现出半透明特性。我们制作并研究了基于 M1 和 M2 的小分子光电探测器（SMPD）。对于以 BCP 作为空穴阻挡层（HBL）的 SMPD，在 -0.1 V 电压下，800 nm 波长处的检测率为 5.0 × 1011 Jones，是已报道的检测率最高的近红外 SMPD 之一。利用足够薄的银电极，首次获得了可见光区平均透射率为 45% 的透明 PD。在 300-900 纳米的宽光谱范围内，这种透明的光致发光器件在 1011-1012 琼斯之间表现出相当稳定和较高的检测率。此外，化合物侧链对器件性能有很大影响，这可能与它们的薄膜吸收系数、分子堆积和活性层形态有关。
• Synthesis and structural, electronic, optical and FET properties of thiophene–pyrrole mixed hexamers end-capped with phenyl and pentafluorophenyl groups
  作者：Tohru Nishinaga、Toshihiko Miyata、Masaki Tateno、Masahide Koizumi、Masayoshi Takase、Masahiko Iyoda、Norihito Kobayashi、Yoshihito Kunugi

  DOI：10.1039/c1jm12966j

  日期：——

  α-Linked thiophene–pyrrole mixed hexamers 3a–5a end-capped with two phenyl, two pentafluorophenyl and both phenyl and pentafluorophenyl units were newly synthesized, and their structural, electronic, optical and FET properties were investigated. Structural analyses by means of X-ray crystallography and theoretical calculations showed that the π-system of the oligomer chains is twisted due to the steric repulsion between the hexyl group of the pyrrole unit and the adjacent thiophene moiety. From comparison of the absorption maxima and redox potentials, end-capping with phenyl and pentafluorophenyl units did not affect the HOMO–LUMO gap for the thiophene–pyrrole hexamer, and the multiple fluorine substituents slightly decreased both HOMO and LUMO levels by the inductive effects of the electronegative fluorine atoms. Although the diphenyl derivative 3a with a herringbone-type packing structure did not serve as an active layer for FET devices, a unique crystal-to-crystal phase transition with a color change from yellow to red was observed upon heating. In contrast to the herringbone-type packing structure of 3a, the unsymmetrical phenyl–pentafluorophenyl derivative 5a showed a partially π-stacked structure, most likely due to dipole–dipole interactions. The π-stacked structure of 5a caused a good hole mobility of 4.1 × 10−2 cm2 V−1s−1 in a single crystal FET device.

  新合成了以两个苯基、两个五氟苯基以及苯基和五氟苯基为端盖的δ-连接噻吩吡咯混合六聚体3aâ5a，并研究了它们的结构、电子、光学和场效应晶体管特性。通过 X 射线晶体学和理论计算进行的结构分析表明，由于吡咯单元的己基与相邻的噻吩分子之间存在立体排斥，低聚物链的Ï-系统是扭曲的。从吸收最大值和氧化还原电位的比较来看，苯基和五氟苯基单元的端封并不影响噻吩吡咯六聚物的 HOMOâLUMO 间隙，而多个氟取代基在电负性氟原子的感应作用下会略微降低 HOMO 和 LUMO 水平。虽然具有人字形填料结构的二苯基衍生物 3a 不能用作场效应晶体管器件的活性层，但在加热时却观察到了独特的晶体-晶体相变，颜色从黄色变为红色。与 3a 的人字形堆积结构不同，不对称的苯基五氟苯基衍生物 5a 显示出部分Ï-堆积结构，这很可能是由于偶极与偶极之间的相互作用。5a 的Ï-堆积结构使其在单晶场效应晶体管器件中具有 4.1 Ã 10â2 cm2 Vâ1sâ1 的良好空穴迁移率。