Engineering Corrole and Porphyrin-Based Multivariate Metal–Organic Frameworks for Si–H Bond Insertion

Inorganic Chemistry, Год журнала: 2024, Номер unknown

Опубликована: Дек. 6, 2024

As a contracted porphyrin analogue, corrole shows more acidic and trinegative/triprotic nature compared with in the field of coordination chemistry. However, direct introduction into metal–organic framework is quite difficult due to its lower C2V symmetry. Herein, we report one-pot synthesis series porphyrin-based multivariate porphyrinic frameworks M1(TCPC)@M2-PCN-222 (M1 = CuIII, MnIII, FeIVCl; TCPC 5,10,15-tris(4-carboxyphenyl) corrole; M2 CoII, CuII, NiII, FeIIICl) applied them insertion Si–H bond α-diazoacetates. The resultant FeCl(TCPC)@Ni-PCN-222 displayed highest efficiency turnover number 796 based on amount Fe, which could be reused at least 5 times without negligible loss activity. Mechanistic studies disclosed that reactivity came from synergistic effect between FeCl(TCPC) Ni-PCN-222, acted as active site formation metal-carbene, whereas Ni-PCN-222 helped condense silane molecules for boosting bond.

Язык: Английский

Synthesis, spectroscopic and electrochemical investigation on the conformational features of meso -5-formylthien-2-ylporphyrins and its terpyridinylthien-2-ylporphyrin and Porphyrin-Corrole dyad

Journal of Sulfur Chemistry, Год журнала: 2023, Номер 45(2), С. 184 - 197

Опубликована: Ноя. 8, 2023

A facile approach for the syntheses of regioselective meso- mono, di (cis and trans), tri formylthien-2-ylporphyrins from meso-tetrathien-2-ylporphyrin (ThP) is presented. The synthesized mono formylthien-2-ylporphyrin ThP-CHO was further functionalized to 5-((5-terpyridinyl)thien-2-yl)-10,15,20-tris(thien-2-yl)porphyrin (ThP-TPy) Porphyrin-Corrole (Por-Cor) dyad. influence formyl substitution functionalization on thien-2-yl ring(s) with porphyrin central π-system examined through UV–Vis absorption, 1H NMR spectroscopy electrochemical studies. red shift Soret band Q bands in absorption spectrum redox potentials are shown be dependent number (ThP-CHO, 424 nm < ThPt-(CHO)2 ThPc-(CHO)2, 425 ThP(CHO)3, 427 nm). significant variation distinct bathochromic series derivatives, ThP-TPy Por-Cor dyad have been explained based near-planar orientation meso-thienyl groups core.

Язык: Английский