Synthesis and self-assembly of a novel tetrapyrrole containing dipyrrin units linked at the 3,3′-positions

“…It possesses similar coordinate properties to its analogues, such as dipyrrin, [18][19][20] and excellent solubility in common solvents. By varying the spacer bridges between two pyrrol-2-ylmethyleneamine units, the resulting bis(pyrrol-2-ylmethyleneamine) ligands can selfassemble to form supramolecules with interesting shapes, such as double-stranded helicates, triangles, and squares.…”

Section: Thementioning

confidence: 99%

Double‐Stranded Helicates, Triangles, and Squares Formed by the Self‐Assembly of Pyrrol‐2‐ylmethyleneamines and Zn^II Ions

Chen

Xiong

et al. 2003

Angew Chem Int Ed

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The metal complexes of ligands I, a pyrrol-2-yl Schiff base or pyrrol-2-ylmethyleneamine, have been known for a long time. [1][2][3] Macrocycles containing pyrrol-2-ylmethyleneamine units, such as texaphyrins and expanded porphyrins, [4] have been extensively investigated. Linear-spacer-bridged bis(pyrrol-2-ylmethyleneamine)s and their complexes with metal ions were recently reported, [5][6][7][8][9] which showed that both the preparation of the ligands and the complexes were highly efficient, and the metal complexes formed by pyrrol-2-ylmethyleneamines possessed good solubility in common solvents. These facts encouraged us to explore their use as a building block for supramolecular self-assembly. In this paper we report the neutral doublestranded helicates, trimeric triangles, and tetrameric squares formed through the self-assembly of spacer-bridged bis(pyrrol-2-ylmethyleneamine) ligands with Zn II ions. Ligands 2-5 were prepared in high yields (Scheme 1) by the condensation of diamines with 4-ethyl-5-formyl-3-methyl-1H-pyrrole-2-carboxylic acid ethyl ester (1) in ethanol. The ligands 2-5 were each reacted with zinc(ii) acetate dihydrate in THF (Scheme 2), to give the complexes 6-9, respectively, in excellent yields. The complexes, isolated as red (6 and 8) or yellow (7 and 9) powders, are soluble in most common organic solvents. Crystals were grown by slowly evaporating their solutions in THF/EtOH (6 and 7), THF/MeOH (8), or THF/ di(ethylene glycol) (9). All of the crystals are stable in the dark under a nitrogen atmosphere, but decomposed quickly in the air.Analysis of the complexes, primarily by MALDI-TOF mass spectrometry, showed that the molecular masses of 6 and 7 were 1105 and 1284, respectively, which corresponds to dimeric complexes with two ligands and two zinc centers. However, the molecular masses of 8 and 9 were found to be 2209 and 1675, which corresponds to a tetrameric complex (four ligands and Zn centers) and trimeric complex (three ligands and Zn centers), respectively.The 1 H NMR spectra of the zinc complexes 6-9 in CDCl 3 show a single set of proton resonances that could be fully assigned, which suggests that they exist as single species in solution. In all cases, the disappearance of the NH protons from the free ligands was observed, which is in agreement Scheme 1. Synthesis and structure of ligands 2-5.Scheme 2. Schematic representation of complexes 6-9.

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“…Dipyrromethenes (dipyrrins) generate fully conjugated, flat monoanionic ligands that coordinate to metal ions to form stable mononuclear complexes [1][2][3][4][5][6][7] with a variety of interesting architectures including discrete helicates [8][9][10][11][12][13][14][15] and coordination polymers [16][17][18][19][20]. Bis(dipyrromethene)s, consisting of two dipyrromethene units joined through a linker, form either dinuclear double-helicates or mononuclear helicates, depending upon the length and conformational preferences of the linker and the coordination geometry preferences of the metal ion [11].…”

Section: Introductionmentioning

confidence: 99%

Heteroleptic zinc dipyrromethene complexes

Amiri¹,

Comeau²,

Thompson³

2006

Journal of Heterocyclic Chemistry

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1 H NMR spectroscopy has been used to study the complexation of a per-alkyl dipyrromethene with zinc acetate. An intermediate, assigned to be the heteroleptic Zn(dipyrromethene)(acetate) complex, is observed under titration conditions although only zinc(dipyrromethene) 2 is obtained after simple work-up. This indicates that disproportionation occurs during work-up and that dipyrromethene complexation does not occur under self-assembled control.

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Synthesis and self-assembly of a novel tetrapyrrole containing dipyrrin units linked at the 3,3′-positions

Cited by 39 publications

References 13 publications

New luminophors based on the binuclear helicates of d-METALS with BIS(DIPYRRIN)S

New luminophors based on the binuclear helicates of d-METALS with BIS(DIPYRRIN)S

Double‐Stranded Helicates, Triangles, and Squares Formed by the Self‐Assembly of Pyrrol‐2‐ylmethyleneamines and Zn^II Ions

Heteroleptic zinc dipyrromethene complexes

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Synthesis and self-assembly of a novel tetrapyrrole containing dipyrrin units linked at the 3,3′-positions

Cited by 39 publications

References 13 publications

New luminophors based on the binuclear helicates of d-METALS with BIS(DIPYRRIN)S

New luminophors based on the binuclear helicates of d-METALS with BIS(DIPYRRIN)S

Double‐Stranded Helicates, Triangles, and Squares Formed by the Self‐Assembly of Pyrrol‐2‐ylmethyleneamines and ZnII Ions

Heteroleptic zinc dipyrromethene complexes

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Double‐Stranded Helicates, Triangles, and Squares Formed by the Self‐Assembly of Pyrrol‐2‐ylmethyleneamines and Zn^II Ions