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首页> 外文期刊>Chemistry: A European journal >Bichromophoric Compounds with Orthogonally and Parallelly Arranged Chromophores Separated by Rigid Spacers
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Bichromophoric Compounds with Orthogonally and Parallelly Arranged Chromophores Separated by Rigid Spacers

机译：具有正交性和平行布置的刚性间隔物分离的BichroRomophoric化合物

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摘要

Electronic energy transfer (EET) between chromophores is of fundamental importance for many biological processes and optoelectronic devices. However, common models fall short in fully describing the process, especially in bichromophoric model systems with a donor and acceptor connected by a rigid linker providing perpendicular geometries. Herein, we report a novel strategy for preparing bichromophores containing adamantane or 2-(2-adamantylidene)- adamantane as rigid spacers, providing a fixed distance between chromophores, and their parallel or perpendicular arrangement without chromophore rotation. New fluorophores were developed and linked via spiroatoms. Bichromophores with identical (blue-blue) or different (bluered) chromophores were synthesized, either in orthogonal or parallel geometry. These were characterized by absorption/ fluorescence spectroscopy, time-resolved fluorescence anisotropy, and fluorescence antibunching measurements. Based on the F?rster point-dipole approximation, EET efficiencies were estimated by using geometrical parameters from (time-dependent) density functional calculations. For bichromophores with parallel geometry, the predicted EET efficiencies were near unity and fit the measurements. In spite of estimated values around 0.4 and 0.5, 100% efficiency was observed also for bichromophores with orthogonal geometry. The new rigid scaffolds presented here open new possibilities for the synthesis of bichormophores with welldefined parallel or perpendicular geometry.
机译：发色团之间的电子能量转移（EET）对许多生物过程和光电器件具有根本重要性。然而，共同模型完全描述了该过程，特别是在具有由提供垂直几何形状的刚性连接器连接的供体和受体的BichroRomophoric模型系统中。在此，我们报告了一种新的制备含有金刚烷或2-（2-亚氨基烷基） - 金刚烷作为刚性隔离物的刚性间隔物的新型策略，在发色团之间提供固定距离，以及它们没有发色团旋转的平行或垂直布置。通过螺旋形成和连接新的荧光团。合成具有相同（蓝色）或不同（蓝色）色团的BichroRomophores，在正交或平行几何形状中合成。这些以吸收/荧光光谱，时间分辨荧光各向异性和荧光抗卷绕测量表征。基于F？罗斯特点偶极近似，通过使用（时间依赖）密度函数计算来估计EET效率。对于具有平行几何形状的BichroRomophores，预测的EET效率接近统一并符合测量。尽管估计值约为0.4和0.5，但对于具有正交几何的BichroRomophores也观察到100％的效率。这里介绍了新的刚性支架，为合成合成的与垂直的平行或垂直几何形状开辟了新的可能性。

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