Coordination Chemistry-Assembled Porphyrinic Catenanes

Abstract

Non covalent [2]catenanes were synthesized in high yield as kinetic products or as thermodynamic products after completion of an equilibrium. These sophisticated architectures were assembled in two steps, from an oblique bis-zinc(II) porphyrin and two different dipyridyl chelates, by using Cu(I)-N interactions to assemble acyclic complexes and Zn(II)-N interactions to generate rings. (1)H NMR including 2D COSY and ROESY experiments were used to characterize each compound. Spectrophotometric titrations highlight the influence of geometry in terms of distances and angles in non covalent coordinated assemblies. In fact, it was proved that a perfect fit leads to highly stable coordination chemistry-assembled species.

Design, Synthesis, and Evaluation of 2,9‐Bis[(substituted‐aminomethyl)phenyl]‐1,10‐phenanthroline Derivatives as G‐Quadruplex Ligands

“…The reported 2,9‐bis[(substituted‐aminomethyl)phenyl]‐1,10‐phenanthroline derivatives 1 a – i were synthesized from the commercially available 2,9‐dichloro‐1,10‐phenanthroline (Schemes and ). The bis‐[2,9‐(formylphenyl)]‐1,10‐phenanthrolines 2 a – c were easily prepared by a direct double‐Suzuki–Miyaura cross‐coupling reaction of 2,9‐dichloro‐1,10‐phenanthroline with 2‐, 3‐ or 4‐formylphenylboronic acid performed in the presence of Pd(PPh 3 ) 4 as a catalyst, and in the presence of potassium (or sodium) carbonate as the base . The structure of 2 b was established by X‐ray crystallography, IR, and 1 H and 13 C NMR data (Figure ).…”

“…The bis- [2,9-(formylphenyl)]-1,10-phenanthrolines 2a-c were easily prepared by ad irect double-Suzuki-Miyaura cross-coupling reactiono f2 ,9-dichloro-1,10-phenanthrolinew ith 2-, 3-or 4-formylphenylboronic acid performed in the presence of Pd(PPh 3 ) 4 as ac atalyst, and in the presence of potassium (or sodium) carbonatea st he base. [30,31] The structure of 2b was established by X-ray crystallography,I R, and 1 H and 13 CNMR data ( Figure 2). Reaction of primary amines with 2a-c gave the di-imines 3a-i,w hich were reduced into the 2,9-bis[(substituted-aminomethyl)phenyl]-1,10-phenanthrolines 1a-i using sodium borohydridei nm ethanola sp reviously described.…”

Chains, Necklaces and Weaving Chain‐link Grids from Self‐Assembly Reactions

“…Silica gel (70-230 mesh) for flash column chromatography was purchased from Aldrich. 2,9-Dichloro-1,10 phenanthroline, [12] ligand 1 [11] and ligand 4 [16] were prepared according to the reported procedures. 1 Ha nd 13 CNMR spectra were recorded with aB ruker Advance 400 spectrometer (400 MHz) at RT.C hemical shifts are given with respect to tetramethylsilane.…”

1,5-(4,4'-Dipyridyl)naphthalene

“…There is currently strong interest in using (4,4'-dipyridyl)naphthalenes for diverse applications in supramolecular chemistry, including the synthesis of flexible pillared metal organic frameworks (MOFs) [1][2][3][4], hydrogen-bonded templates for supramolecular structures prepared by mechanochemistry used for solid-state photodimerization reactions [5][6][7][8][9] and the stabilization of porphyrinic catenanes [10,11]. To date, only four isomers of the parent (4,4'-dipyridyl)naphthalenes (Scheme 1, molecular formula C22H16N2) have been reported in the literature: 1,4-, 1 [1], 1,8-, 2 [5-9] 2,7-, 3 [10,11] and 2,6-, 4 [2][3][4].…”

“…To date, only four isomers of the parent (4,4'-dipyridyl)naphthalenes (Scheme 1, molecular formula C22H16N2) have been reported in the literature: 1,4-, 1 [1], 1,8-, 2 [5-9] 2,7-, 3 [10,11] and 2,6-, 4 [2][3][4]. Herein we report the preparation, characterization and structure determination by single-crystal X-ray diffraction of the new 1,5-isomer, 5.…”