Issue 30, 2015

Discrete and polymeric complexes of a macrocyclic pillar ligand in the absence and presence of dicarboxylic acid coligands

Abstract

The macrocyclic pillar ligand, dipyridyldibenzotetraaza[14]annulene (H2L), in the absence and presence of the dicarboxylate coligands, biphenyl-4,4′-dicarboxylic acid (H2bpdc) or benzene-1,3-dicarboxylic acid (H2bdc), reacts with nickel(II), cobalt(II) and zinc(II) to yield [Ni(L)] (1), [Co(L)] (2), [Co(L)]n (3), {[Zn(H2L)(bdc)]·0.5DMF·1.5H2O}n (4) and {[Co4(L)2(bpdc)2]·2DMF·H2O}n (5) displaying both discrete and polymeric structures. Complexes 1 and 2 are isostructural, with the respective low-spin, square-planar metal ions occupying the macrocyclic cavity and bound to the N4-donor set of the macrocycle in its doubly deprotonated form. In 3, the cobalt(II) centre again occupies the macrocyclic cavity, but in this case one axial site is occupied by a pyridyl nitrogen from a second ligand complex, resulting in the formation of an infinite zigzag one-dimensional (1D) structure. Solvothermal reaction between Zn(NO3)2·4H2O, H2L and H2bdc afforded the 2D coordination polymer {[Zn(H2L)(bdc)]·0.5DMF·1.5H2O}n (4) in which H2L ligands crosslink 1D (bdc-Zn)n wavy backbones via Zn–Npyd bonds. In contrast, the solvothermal reaction of H2L with Co(NO3)2·6H2O in the presence of H2bpdc resulted in formation of the 2-fold interpenetrated 3D coordination polymer, {[Co4(L)2(bpdc)2]·2DMF·H2O}n (5), exhibiting a pillared-layer structure. The 3D framework of 5 is based on dicobalt(II) cluster secondary building units (SBUs) to yield a rob net in which the bpdc/Co-based 2D nets are cross-linked by CoL macrocyclic pillar units; the framework of 5 is thermally stable until 350 °C.

Graphical abstract: Discrete and polymeric complexes of a macrocyclic pillar ligand in the absence and presence of dicarboxylic acid coligands

Supplementary files

Article information

Article type
Paper
Submitted
10 Jun 2015
Accepted
26 Jun 2015
First published
29 Jun 2015

CrystEngComm, 2015,17, 5717-5724

Discrete and polymeric complexes of a macrocyclic pillar ligand in the absence and presence of dicarboxylic acid coligands

H. Ryu, Y. Mulyana, I. Park, J. Kim, L. F. Lindoy and S. S. Lee, CrystEngComm, 2015, 17, 5717 DOI: 10.1039/C5CE01127B

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements