Kalaiselvan Arumugam, Naniyil Athira, Ipe Ruth Mariam, Krishna Isukapalli Sai Vamsi, Vennapusa Sivaranjana Reddy, Andrews Alex P, Gokulnath Sabapathi
School of Chemistry, Indian Institute of Science Education and Research Thiruvananthapuram, Thiruvananthapuram, Kerala 695551, India.
J Org Chem. 2023 Oct 20;88(20):14377-14387. doi: 10.1021/acs.joc.3c01255. Epub 2023 Oct 3.
A new class of N-confused porphyrin embedded with a carbazole subunit was prepared via [3 + 1] acid-catalyzed condensation of appropriate precursors. underwent smooth metal complexation with Pd(II) and Cu(II) salts to provide the corresponding diamagnetic and paramagnetic , respectively. The single-crystal X-ray structure of is evident with a square-planar Pd-center through C-H activation of inverted pyrrole. Superconducting quantum interference device analysis combined with electron paramagnetic resonance (EPR) results provided insights into the paramagnetic nature of . Further, a ratiometric enhancement of near-IR fluorescence at 746 nm was found to be reversible upon adding CN and F ions. The solid-state structure of confirms that the anionic species is due to NH deprotonation.
通过适当前体的[3 + 1]酸催化缩合反应制备了一类嵌入咔唑亚基的新型N-稠合卟啉。其分别与Pd(II)和Cu(II)盐顺利进行金属络合反应，分别得到相应的抗磁性和顺磁性产物。通过对倒置吡咯进行C-H活化，具有平面正方形Pd中心的产物的单晶X射线结构清晰可见。超导量子干涉装置分析与电子顺磁共振（EPR）结果相结合，深入了解了产物的顺磁性质。此外，发现加入CN和F离子后，746 nm处近红外荧光的比例增强是可逆的。产物的固态结构证实阴离子物种是由于NH去质子化所致。
