Synthesis, Structure, and Properties of Helical Bis-Cu(II) Complex of Linear Hexapyrrolic Ligand.

Abstract

The chemistry of metal helical complexes has attracted wide interest not only because of their resemblance with DNA structure but also due to their unique photophysical and chiroptical properties. Linear hexapyrrolic ligand 1 has been designed and synthesized using 3-pyrrolyl BODIPY as a key precursor. The reactivity of the appended pyrrole group of 3-pyrrolyl BODIPY was taken as an advantage to synthesize bis(3-pyrrolyl BODIPY) by treating 3-pyrrolyl BODIPY with 10 equiv of acetone in CHCl3 under acid-catalyzed conditions and afforded bis(3-pyrrolyl BODIPY) 2 in 20% yield. Bis(3-pyrrolyl BODIPY) 2, in which two 3-pyrrolyl BODIPY units were connected via sp3 meso carbon, was very stable, and its identity was confirmed by HR-MS, NMR, and X-ray crystallographic analysis. The X-ray structure revealed that the 3-pyrrolyl BODIPY moieties in bis(3-pyrrolyl BODIPY) 2 remained almost planar and arranged at an angle of 98.4° with each other, leading to a V-shaped conformation. In the next step, bis(3-pyrrolyl BODIPY) 2 was treated with AlCl3 in acetonitrile/methanol at reflux to afford hexapyrrolic ligand 1. Hexapyrrolic ligand 1 was treated with CuCl2 in acetonitrile at room temp for 1 h followed by crystallization to afford helical bis-Cu(II) complex 1-Cu. Bis-Cu(II) complex 1-Cu was characterized and studied by HR-MS, X-ray crystallography, ESR, absorption, and DFT/TD-DFT techniques. The X-ray structure revealed that the bis-Cu(II) complex was a double-stranded bimetallic helicate and each Cu(II) ion was coordinated to four nitrogen atoms of two dipyrrin units from two hexapyrrolic ligands in a distorted tetrahedral geometry. The crystal packing diagram showed that the bis-Cu(II) complex formed as a racemic mixture containing both M and P isomers which was unable to isolate. The ESR spectrum of bis-Cu(II) complex 1-Cu indicated the presence of two noninteracting Cu(II) ions in slightly different coordination environments. DFT and TD-DFT studies were in agreement with the experimental observations of bis(3-pyrrolyl BODIPY) 2 complex and bis-Cu(II) complex 1-Cu.