Creation of the cross type electron conjugated system strong fluorophore arranged donor- and acceptor- groups

创建交叉型电子共轭系统强荧光团排列的供体和受体基团

• 批准号: 18550133
• 负责人: MATSUBARA Yoshio
• 金额: $ 2.53万
• 依托单位: Kinki University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2006
• 资助国家: 日本
• 起止时间: 2006 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-18550133/
• 关键词: Strong fluorophores; Donor group; Acceptor group; Cross type; Electron conjugated system; Core part in the center; Photophysical data

In this study, creation of strong fluorescence material was carried out by the constriction of π-electron conjugation system forming core part in the center, arm part having electron donor or acceptor group in four direction, and result were discussed with photophysicochemically. The design of emitted cross shaped tetrakis(phenyletylnyl)benzenes: The cross types of electron conjugative ability was advantageous than a straight line type by the investigation of HOMO-LUMO gap using AM1 calculation. Thus, compounds 1-4 were designed and synthesized. Compounds 1-4 by the reaction of halogenated 1, 4-disubstituted-benzene(core part) with p-substituted phenyl ethynyl (arm part) were synthesized using sonogashira cross coupling reaction. Photophysical data of cross shaped tetrakis(phenylethynyl)benzenes were summarized. Absorption(λ_<abs>) and absorbancy (log ε) were increase in order of non-substitution compound(1) < electron donor(core) compound(2) < electron acceptor(side arms) compound(3) < electron donor(core)/acceptor(side arms) compound(4) and emission wavelength(λ_<em>) were red-shifted above orders. The fluorescence quantum yields (Φ_f) also greatly go up by the introducing the electronic donor acceptor group . The compound 1, 2, 3 and 4 increase the k_r values, and decrease the k_d values. Relationship exists between Φ_f and kinetic parameters for the radiative and radiationless process were examined. ΔΔS^‡=ΔS_r^‡-ΔS_d^‡=1n k_r/k_dA nice liner relationship between Φ_f and ΔΔS^‡(Φ_f= 0.092ΔΔS^‡+ 0.520). It is inferred that ΔΔS^‡ might be a measure for α-conjugation of the molecules at the exited singlet state.

本研究通过π电子共轭体系的收缩，在中心形成核心部分，臂部分在四个方向上具有电子给体或受体基团，从而实现了强荧光材料的制备，并对结果进行了化学分析。四（苯基乙炔基）苯的十字形发光设计：通过对HOMO-LUMO能隙的AM 1计算，发现十字形的电子共轭能力优于直线形。因此，设计并合成了化合物1-4。以卤代1，4-二取代苯（核部分）和对取代苯乙炔（臂部分）为原料，通过Sonogashira交叉偶联反应合成了化合物1-4。总结了十字形四苯乙炔基苯的光物理数据。吸光度（λ_<abs>）和吸光度（log ε）按未取代化合物（1）&lt;电子给体（核心）化合物（2）&lt;电子受体（侧臂）化合物（3）&lt;电子给体（核心）/受体（侧臂）化合物（4）的顺序增加，发射波长（λ_<em>）在上述顺序上发生红移。荧光量子产率（Φ_f）也因电子给体受体基团的引入而大大提高。化合物1、2、3和4使k_r值增大，k_d值减小。研究了有辐射和无辐射过程中Φ f与动力学参数的关系。ΔΔS^f =ΔS_r^f-ΔS_d^f = 1 n k_r/k_d Φ_f与ΔΔS^f之间存在良好的线性关系（Φ_f= 0.092ΔΔS^f + 0.520）。我们推测ΔΔS^ε可能是分子在激发单重态时α共轭的一个量度。

项目成果

Solid-state optical properties of a chiral supramolecular fluorophore consisting of chiral(1R, 2R)-1, 2-diphenylethyleneiamine and fluorescent carboxylic acid derivatives

由手性(1R,2R)-1,2-二苯基乙二胺和荧光羧酸衍生物组成的手性超分子荧光团的固态光学性质

• 发表时间: 2007
• 期刊: Tetrahedron Lett. 48(16)
• 作者: Y. Imai;K. Kawaguchi;T. Harada;T. Sato;M. Ishikawa;M. Fujiki;R. Kuroda;Y. Matsubara
• 通讯作者: Y. Matsubara

New Fluorophores with Rod-Shaped Polycyano π-Conjugated Structures : Synthesis and Photophysical Properties.

具有棒状多氰基 π 共轭结构的新型荧光团：合成和光物理性质。

• 发表时间: 2006
• 期刊: Org. Lett. 8(4)
• 作者: Y. Yamaguchi;T. Ochi;T. Wakamiya;Y. Matsubara;Z. Yoshida
• 通讯作者: Z. Yoshida

Rod-shaped oligophenyleneethynylenes modified by donor and acceptor groups inablock mamer:synthesis and light-emitting characteristics

嵌段给体和受体基团修饰的棒状低聚亚苯基亚乙炔基：合成和发光特性

• 发表时间: 2007
• 期刊: Chem.Lett 36(6)
• 作者: Y. Imai;K. Kawaguchi;T. Harada;T. Sato;M. Ishikawa;M. Fujiki;R. Kuroda;Y. Matsubara;Y.Imai;T.Ochi
• 通讯作者: T.Ochi

分子中央に電子吸引基を有するドナー/アクセプター置換オリゴフェニレンエチニレン類:合成と発光特性

分子中心带有吸电子基团的供体/受体取代的低聚亚苯基亚乙炔基：合成和发光性能

• 发表时间: 2007
• 作者: Y.Yamaguchi;T.Ochi;S.Myyamura;T.Tanaka;S.Kobayashi;T.Wakamiya;Y.Matusbara;Z.Yoshida;越智 剛敬
• 通讯作者: 越智 剛敬

Rigid Molecular Architectures That Comprise a 1, 3, 5-Trisubstituted Benzene Core and Three Oligoarylene-ethynylene Arms : Light-Emitting Characteristics and π Conjugation between the Arms.

包含 1, 3, 5-三取代苯核和三个低聚亚芳基-乙炔臂的刚性分子结构：发光特性和臂之间的 π 共轭。

• 发表时间: 2006
• 期刊: J. Am. Chern,Soc 128(14)
• 作者: Y. Yamaguchi;T. Ochi;S. Miyamura;T. Tanaka;S. Kobayashi;T. Wakamiya;Y. Matsubara;Z. Yoshida
• 通讯作者: Z. Yoshida