Wolff Shana A, Alemán Elvin A, Banerjee Debasish, Rinaldi Peter L, Modarelli David A
Department of Chemistry, Knight Chemical Laboratory, The University of Akron, Akron, Ohio 44325-3601, USA.
J Org Chem. 2004 Jul 9;69(14):4571-6. doi: 10.1021/jo049621r.
Three disubstituted N-confused porphyrins (2-4) were prepared in ca. 4% yield using a one-pot synthesis. These porphyrins bear 3,5-di-tert-butylphenyl groups substituted at the C(5) and C(20) meso positions and para-substituted (Br, NO(2), ethynyl) phenyl groups at the C(10) and C(15) meso positions. The specific orientation of the aryl rings around the macrocycle in porphyrin 2 was definitively determined using a combination of 1D ((1)H and (13)C) and 2D (gHMQC and gHMBC) NMR spectroscopy. The absorption spectra of 2-4 in CH(2)Cl(2) and dimethylacetamide are similar to those of N-confused tetraphenylporphyrin in the same solvents but have Soret and Q-bands that are shifted to lower energies. Steady-state fluorescence measurements revealed Q(x)(0,0) and Q(x)(0,1) bands similar in energy to the unsubstituted NCPs 1i and 1e. The fluorescence quantum yield results for two of these NCPs (2, 4) are atypical of porphyrin behavior and are being further investigated by time-resolved spectroscopy.
通过一锅法合成制备了三种二取代的N-杂卟啉（2-4），产率约为4%。这些卟啉在C(5)和C(20)中位带有3,5-二叔丁基苯基，在C(10)和C(15)中位带有对位取代（Br、NO(2)、乙炔基）苯基。使用一维（(1)H和(13)C）和二维（gHMQC和gHMBC）核磁共振光谱相结合的方法，明确确定了卟啉2中环周围芳基环的特定取向。2-4在CH(2)Cl(2)和二甲基乙酰胺中的吸收光谱与相同溶剂中N-杂四苯基卟啉的吸收光谱相似，但Soret带和Q带的能量发生了红移。稳态荧光测量显示，Q(x)(0,0)和Q(x)(0,1)带的能量与未取代的NCPs 1i和1e相似。其中两种NCPs（2, 4）的荧光量子产率结果不符合卟啉的典型行为，目前正在通过时间分辨光谱进行进一步研究。
