Unprecedented Strong Panchromic Absorption from Proton-Switchable Iridium(III) Azoimidazolate Complexes.
Unprecedented Strong Panchromic Absorption from Proton-Switchable Iridium(III) Azoimidazolate Complexes.
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DOI：
10.1002/chem.201503546
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发表时间：
2015-12
期刊：
影响因子：
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通讯作者：
Adam F Henwood;Yueging Hu;M. Sajjad;G. K. V. Thalluri;Sanjay S. Ghosh;D. Cordes;A. Slawin;I. Samuel;N. Robertson;E. Zysman‐Colman
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文献类型：
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作者：
Adam F Henwood;Yueging Hu;M. Sajjad;G. K. V. Thalluri;Sanjay S. Ghosh;D. Cordes;A. Slawin;I. Samuel;N. Robertson;E. Zysman‐Colman
报道了两种新的含芳基重氮咪唑配体的杂电性铱（III）配合物。这些配合物在结构上不同于咪唑环的质子化状态，但可以通过改变合成条件独立地获得。它们的结构已被x射线晶体结构分析明确证实，两种配合物的结构参数有惊人的差异。游离重氮咪唑配体的强吸收性质在这些铱配合物中得到增强，质子化阳离子配合物在700 nm处表现出非常强的全色吸收。去质子化的中性配合物的吸收谱被蓝移了约100 nm，因此两种配合物之间的相互转化作为环境酸度/碱度的函数可以很容易地通过吸收光谱来监测。理论计算揭示了这些明显不同的吸收特性的起源。最后，质子化类似物被定位为有机光伏（OPV）应用的受体材料，并报道了初步结果。
Two new heteroleptic iridium(III) complexes bearing an aryldiazoimidazole ligand are reported. These complexes differ structurally with respect to the protonation state of the imidazole ring, but can be independently accessed by varying the synthetic conditions. Their structures have been unequivocally confirmed by X-ray crystal structure analysis, with surprising differences in the structural parameters of the two complexes. The strongly absorbing nature of the free diazoimidazole ligand is enhanced in these iridium complexes, with the protonated cationic complex demonstrating extraordinarily strong panchromic absorption up to 700 nm. The absorption profile of the deprotonated neutral complex is blueshifted by about 100 nm and thus the interconversion between the two complexes as a function of the acidity/basicity of the environment can be readily monitored by absorption spectroscopy. Theoretical calculations revealed the origins of these markedly different absorption properties. Finally, the protonated analogue has been targeted as an acceptor material for organic photovoltaic (OPV) applications, and preliminary results are reported.