During the course of exploring crystallization conditions in generating metal–organic frameworks (MOFs) for use in the crystalline sponge method, two discrete metal–organic complexes, namely, aqua[2,4,6-tris(pyridin-4-yl)-1,3,5-triazine]zinc(II) bromide, [Zn(C18H12N6)(H2O)]Br2, and aqua[2,4,6-tris(pyridin-4-yl)-1,3,5-triazine]zinc(II) chloride, [Zn(C18H12N6)(H2O)]Cl2, were encountered. Structures in the orthorhombic space groupPnma(No. 62) for the bromide congener at 299 K and the chloride congener at 100 K were obtained. A phase transition for the bromide congener occurred upon cooling from 299 to 100 K, yielding a crystal polymorph with four domains that exhibits monoclinicP21/mspace-group symmetry (No. 11), which arises from conformational changes. The main intramolecular contacts that contribute to the crystal packing in all observed structures are H...H, Halide...H/H...Halide, C...H/H...C, and N...H/H...N. Intramolecular hydrogen bonding between the Zn-bound water and non-Zn-bound pyridyl N atoms is a prominent feature within the three-dimensional networks. Aromatic π-stacking between the non-Zn-bound pyridine rings and contacts involving the halide ligands further stabilize the crystal packing.
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A Series of Zinc Mononuclear Complexes with Imidoyl Amidine Ligands: Syntheses, Crystal Structures, and Photoluminescence Properties
Three amidine-based ligands were used in the crystal design of a series of mononuclear Zn(II) complexes. Interaction of zinc chloride, ZnCl2, with N-2-pyridylimidoyl-2-pyridylamidine (Py2ImAm) resulted in complexes [Zn(Py2ImAm)2] (1) and [ZnCl2(Py2ImAm)] (2). In [Zn(Py2ImAm)2] (1, monoclinic, P21/c), the metal ion was coordinated with the bidentate pocket of the anionic form of Py2ImAm, while in [ZnCl2(Py2ImAm)] (2, monoclinic, P21/n), the tridentate coordination to a neutral Py2ImAm was completed by two chloride anions. This structural variation was achieved by a pH-controlling strategy using the weak base triethylamine (TEA). Otherwise, three ionic complexes were obtained with 2-amidinopyridine (PyAm) and Zinc(II), [ZnCl(PyAm)2]Cl (3, triclinic, P-1), [ZnCl(PyAm)2]2[ZnCl4]·C2H5OH (4, monoclinic, P21/n), and [ZnCl(PyAm)2]2Cl·CH3OH (5, triclinic, P-1). They comprised the same [ZnCl(PyAm)2]+ monocation with a butterfly-like shape provided by the bidentate chelate coordination of two PyAm neutral entities and a chloride ligand. In a similar butterfly shape, ionic complex [ZnCl(PmAm)2]2[ZnCl4] (6, monoclinic, C2/c) comprised the mononuclear [ZnCl(PmAm)2]+ cations with two bidentate chelate-coordinated 2-amidinopyrimidine (PmAm) as neutral ligands. The Zn(II) pentacoordinated arrangement in 3–6 was variable, from square pyramidal to trigonal bipyramidal. The reported compounds’ synthetic protocols, crystal structures and photoluminescence properties are discussed.
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- Award ID(s):
- 2122108
- PAR ID:
- 10589557
- Publisher / Repository:
- MDPI
- Date Published:
- Journal Name:
- Chemistry
- Volume:
- 6
- Issue:
- 4
- ISSN:
- 2624-8549
- Page Range / eLocation ID:
- 760 to 772
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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