C3-symmetric, dendritic structured, chiral chromophores: synthesis and linear and nonlinear optical properties

C3 对称、树枝状结构、手性发色团：合成以及线性和非线性光学性质

• 批准号: 248121583
• 负责人: Professor Dr. Jürgen Heck
• 金额: --
• 依托单位: Institut für Anorganische und Angewandte Chemie
• 依托单位国家: 德国
• 项目类别: Research Grants
• 财政年份: 2013
• 资助国家: 德国
• 起止时间: 2012-12-31 至 2016-12-31
• 项目状态: 已结题
• 来源: https://gepris.dfg.de/gepris/projekt/248121583?language=en
• 关键词: C3; symmetric; dendritic; structured; chiral

The synthesis of new multifunctional molecular materials is one of the current challenges in synthetic chemistry. This proposal just meets the challenge. On the one side C3 symmetric, dipolar, dendritic structured chromophores with coordinated dia- and paramagnetic metal atoms will be synthesized and their first hyperpolarizability beta will be determined. On the other side these compounds should be chiral in order to study the circulardichroism depending on the second harmonic generation (SHG-CD) and magnetization induced frequency doubling (MSHG) as well as magnetochiral dichroism. Additionally, as another magnetically induced effect, the Faraday rotation of these complexes will be investigated. The metal atoms fix a helical chiral arrangement of the NLO chromophores through chelating coordination and the paramagnetism is believed to enhance the magnetic effects. For the chelating coordination the dipolar single strand NLO chromophore is decorated with 2,2'-bipyridine (bipy) and 2-phenylpyridine (ppy). The substitution of the chelating ligands with electron donating and electron accepting functions in 5 and 5'-position is of particular importance to warrant the communication between the donor and acceptor, and to warrant the dipolar character. The first hyperpolarizability beta will be determined by hyper-Rayleigh scattering with our own set-up, which was provided from the DFG for another project. The HRS set-up is equipped with a Nd:YAG laser and an OPO, which allows to tune the stimulating wavelength (1064 - 1500 nm). Measurements concerning the SHG-CD and the magnetically induced effects will be performed in close collaboration with Verbiest's group at the University of Leuven (Belgium).

新型多功能分子材料的合成是当前合成化学面临的挑战之一。这一建议正好应对了挑战。在一侧，将合成具有配位的双和顺磁性金属原子的C3对称的、偶极的、树枝状结构的发色团，并且将确定它们的第一超极化率β。另一方面，这些化合物应该是手性的，以便研究取决于二次谐波产生（SHG-CD）和磁化诱导倍频（MSHG）的圆二色性以及磁手性二色性。此外，作为另一种磁感应效应，我们还研究了这些配合物的法拉第旋转。金属原子通过螯合配位固定NLO发色团的螺旋手性排列，并且顺磁性被认为增强了磁性效应。对于螯合配位，偶极单链NLO发色团用2，2 '-联吡啶（bipy）和2-苯基吡啶（ppy）修饰。螯合配体在5和5 '-位上被电子给予和电子接受官能团取代对于保证供体和受体之间的通信以及保证偶极特性是特别重要的。第一个超极化率β将由超瑞利散射与我们自己的设置，这是从DFG提供的另一个项目确定。HRS装置配备有Nd：YAG激光器和OPO，可调节刺激波长（1064 - 1500 nm）。关于SHG-CD和磁感应效应的测量将与比利时鲁汶大学的Verbiest小组密切合作进行。

项目成果

Donor‐Acceptor Substituted 2‐Phenylpyridines by Means of Reductive C,C–Cross Coupling Reaction

• DOI: 10.1002/slct.201600707
• 发表时间: 2016-08
• 作者: Sebastian Triller;Tim Dittmann;M. Bendig;Jan Schnelle;Tom Friedmann;J. Heck