High Fidelity Self-Sorting Assembling ofmeso-Cinchomeronimide Appendedmeso-mesoLinked Zn(II) Diporphyrins

Abstract

In noncoordinating solvents, meso-cinchomeronimide appended Zn(II) porphyrin 2 forms a cyclic trimer, while diporphyrins 7 exhibit high-fidelity self-sorting assembling to form discrete cyclic trimer, tetramer, and pentamer with large association constants from 7(in-in), 7(in)(-)(out), and 7(out-out), respectively, through almost perfect discrimination of enantiomeric and conformational differences of the meso-cinchomeronimide substituents. In the latter self-sorting processes, the dihedral angles dictated by the two pyridyl nitrogen atoms control the size of the aggregates; the trimer from 7(in-in), the tetarmer from 7(in)(-)(out), and the pentamer from 7(out-out). Cyclic structures of (2)(3) and (R-7(out-out))(5) have been determined by single-crystal X-ray diffraction analysis.

Supramolecular Coordination: Self-Assembly of Finite Two- and Three-Dimensional Ensembles

“…520 The homochiral self-sorting behaviors of meso -cinchomeronimide (3,4-pyridinedicarboximide)-appended Zn(II)-porphyrin and 10,10′-cinchomeronimide-appended meso - meso linked Zn(II)-diporphyrins in noncoordinating solvents were also investigated. 668 While the former undergoes complete assembly to yield its trimer, the latter led to trimeric, tetrameric, and pentameric rings, through rigorous homochiral self-sorting processes, owing to the presence of three stable conformers with respect to the orientation of the pyridyl nitrogen atoms. Similarly, meso-meso ’-bis(5-azaindol-2-yl)-appended Zn(II)-porphyrin formed a trimeric fluorescent assembly that consisted of three single atropisomers due to the facile rotation of the 5-azaindol-2-yl substituent and effective trapping via self-sorting assembling by complementary coordination.…”

Supramolecular Organization of Porphyrins and Phthalocyanines by Use of Biomimetic Coordination Methodology

“…When cinchomeronimide was introduced into the meso-meso directly linked bisporphyrin 79, six possible atropisomers of axially chiral 79 were individually assembled into triple, quadruple and pentameric strands through homochiral self-sorting behavior. 127 The binding constants for α,α-79 3 , α,β-79 4 and β,β-79 5 large binding constants allowed chiral resolution by chiral high performance liquid chromatography (HPLC). Similar homochiral self-sorting phenomena were reported for 5-azaindol-2-yl-appended bisporphyrin.…”

Subporphyrins: A Legitimate Ring-Contracted Porphyrin with Versatile Electronic and Optical Properties

“…7 (2011)angles are higher than those of subporphyrins with orthounsubstituted meso-aryl groups. 19 F NMR spectroscopy revealed hindered rotation of the meso-pentafluorophenyl groups in 71 even at 140°C in solution. Since subporphyrin 72 cannot be synthesized by our Alder-type protocol from 1-(tri-1-pyrrolylboryl)pyridine 6, this extrusion reaction is synthetically important.…”