cg4011289_si_004.cif (39.74 kB)
A Novel Porphyrin-Based Ligand Containing Four 4,4′-Dipyridylamine Moieties: Syntheses, Structures, and Luminescent Properties of Mn(II), Cu(II), Zn(II), and Cd(II) Coordination Polymers
dataset
posted on 2013-10-02, 00:00 authored by Quanzheng Zha, Caixia Ding, Xing Rui, Yongshu XieThe design and syntheses of porphyrin-based
ligands are attractive
for creating coordination assemblies with novel structures and intriguing
properties. In this work, we designed and synthesized a novel porphyrin-based
ligand 5,10,15,20-tetrakis(4,4′-dipyridylaminophenylene)porphyrin
(TDPAP, H2L) by the introduction of four peripheral 4,4′-dipyridylamine
moieties to a porphyrin platform. Starting from this novel ligand,
the protonated form of the ligand H4LCl2·2CH3OH·2H2O (1) and four coordination
polymers [Mn(III)Mn(II)LCl3(DMF)]n (2), [Cu4L(CH3COO)5(HCOO)(CH3COOH)(H2O)3]n·nCH3COOH·nH2O (3), [Zn3L(CH3COO)4]n (4), and [Cd2H2L(CH3COO)4]n·nDMF·nCH3COOH·2nH2O (5) were synthesized. Single crystal X-ray diffraction analyses revealed
that a rich structural diversity was observed for these compounds
due to the coordination of the multiple peripheral pyridines as well
as the porphyrin core. 1 displays a hydrogen bonded one-dimensional
(1D) structure composed of [(H2O)2Cl2]2– moieties. Complex 2 shows interpenetrated
two-dimensional (2D) coordination networks, which are further linked
by π···π stacking interactions to afford
a three-dimensional (3D) structure. 3 shows a 2D sheet
composed of 50- and 70-membered metallomacrocycles. In complex 4, 1D zigzag coordination chains were generated and further
linked to form a 2D structure. Complex 5 has a stairlike
2D structure formed by the linkage of 1D coordination chains through
the bridging of binuclear [Cd2(CO2)4] subunits. In these compounds, TDPAP shows a unique coordination
behavior. It may bind 4–7 metal centers, and it demonstrates
conformational flexibility and the ability to form intermolecular
hydrogen bonds and π···π interactions,
which contribute to the formation of novel supramolecular structures.
On the basis of the novel structures, the solid state emissions of
the compounds were also investigated.