Near-infrared luminescent Sn(IV) complexes of N-confused tetraphenylporphyrin: Effect of axial anion coordination
Near-infrared luminescent Sn(IV) complexes of N-confused tetraphenylporphyrin: Effect of axial anion coordination
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DOI：
10.1142/s1088424615500212
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发表时间：
2015-04
影响因子：
1.5
通讯作者：
A. Basu;M. Kitamura;Shigeki Mori;Masatoshi Ishida;Yongshu Xie;H. Furuta
中科院分区：
文献类型：
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作者：
A. Basu;M. Kitamura;Shigeki Mori;Masatoshi Ishida;Yongshu Xie;H. Furuta
合成了具有不同轴向配体的 N 混杂四苯基卟啉的新型锡（IV）卤配合物，并通过包括 X 射线晶体学分析在内的各种光谱方法进行了表征。二氯和二溴衍生物的分子结构具有完美的八面体几何形状，几乎与相应的规则卟啉配合物相当。相反，通过相同的反应方式获得的碘化物/三碘化物络合物表明，锡（IV）阳离子稍微向轴向配位的碘化物阴离子移位，由于N-混淆的卟啉配体的互变异构形式而产生不同的电子结构。这些结构差异反映了不同的光物理和电化学特性。 Sn(IV)配合物具有接近红外发光的能力，然而锡(IV) N-混淆卟啉配合物中碘化物和三碘化物阴离子的不对称轴向配位特别允许更长的发射寿命和更小的单重态-三重态能隙，这通过稳态和时间分辨光谱以及理论计算进行了研究。
Novel tin(IV) halo complexes of an N-confused tetraphenylporphyrin with different axial ligands have been synthesized and characterized by various spectroscopic methods including X-ray crystallographic analysis. The molecular structures of the dichloro and dibromo derivatives possess perfect octahedral geometries, which are nearly comparable to the corresponding regular porphyrin complexes. In contrast, the iodide/triiodide complex obtained by a same reaction manner, demonstrated that the tin(IV) cation is slightly displaced towards axially coordinated iodide anion, giving rise to the different electronic structure due to the tautomeric form of N-confused porphyrin ligand. These structural differences reflected to the distinct photophysical and electrochemical properties. The Sn(IV) complexes are near IR luminescent, however the unsymmetrical axial coordination of iodide and triiodide anions in the tin(IV) N-confused porphyrin complex allows, in particular, the longer emission lifetimes and a smaller singlet-triplet energy gap, which were investigated by steady-state and time- resolved spectroscopies as well as theoretical calculations.