Rota Martir Diego, Hedley Gordon J, Cordes David B, Slawin Alexandra M Z, Escudero Daniel, Jacquemin Denis, Kosikova Tamara, Philp Douglas, Dawson Daniel M, Ashbrook Sharon E, Samuel Ifor D W, Zysman-Colman Eli
Organic Semiconductor Centre, EaStCHEM School of Chemistry, University of St Andrews, St Andrews, Fife, KY16 9ST, UK.
Organic Semiconductor Centre, SUPA, School of Physics and Astronomy, University of St Andrews, St Andrews, Fife, KY16 9SS, UK.
Dalton Trans. 2016 Nov 1;45(43):17195-17205. doi: 10.1039/c6dt02619b.
We present the first examples of dynamic supramolecular systems composed of cyclometalated Ir(iii) complexes of the form of [Ir(C^N)(N^N)]PF (where C^N is mesppy = 2-phenyl-4-mesitylpyridinato and dFmesppy = 2-(4,6-difluorophenyl)-4-mesitylpyridinato and N^N is 4,4':2',2'':4'',4'''-quaterpyridine, qpy) and zinc tetraphenylporphyrin (ZnTPP), assembled through non-covalent interactions between the distal pyridine moieties of the qpy ligand located on the iridium complex and the zinc of the ZnTPP. The assemblies have been comprehensively characterized by a series of analytical techniques (H NMR titration experiments, 2D COSY and HETCOR NMR spectra and low temperature H NMR spectroscopy) and the crystal structures have been elucidated by X-ray diffraction. The optoelectronic properties of the assemblies and the electronic interaction between the iridium and porphyrin chromophoric units have been explored with detailed photophysical measurements, supported by time-dependent density functional theory (TD-DFT) calculations.
我们展示了由[Ir(C^N)(N^N)]PF形式的环金属化Ir(III)配合物（其中C^N为mesppy = 2-苯基-4-均三甲苯基吡啶基和dFmesppy = 2-(4,6-二氟苯基)-4-均三甲苯基吡啶基，N^N为4,4':2',2'':4'',4'''-四吡啶，qpy）与四苯基卟啉锌(ZnTPP)组成的动态超分子体系的首个实例，该体系通过位于铱配合物上的qpy配体的远端吡啶部分与ZnTPP的锌之间的非共价相互作用组装而成。通过一系列分析技术（1H NMR滴定实验、二维COSY和HETCOR NMR光谱以及低温1H NMR光谱）对组装体进行了全面表征，并通过X射线衍射阐明了晶体结构。通过详细的光物理测量，并在含时密度泛函理论(TD-DFT)计算的支持下，探索了组装体的光电性质以及铱和卟啉发色团单元之间的电子相互作用。
