Zn(II)/Cd(II) Terephthalate Coordination Polymers Incorporating Bi-, Tri-, and Tetratopic Phenylamine Derivatives: Crystal Structures and Photoluminescent Properties

Abstract

Using reticular chemistry allowed the design and construction of four novel Zn(II)/Cd(II) coordination polymers, {[Zn(BTPA)(TPA)]•H 2 O} n (1), {[Zn(TTPA)(TPA)]•H 2 O} n (2), {[Cd 2 (TTPA) 2 (TPA) 2 (DMF)]•2H 2 O} n (3), and {[Cd(TTPBDA)-(TPA)] 0.5 •DMF•H 2 O} n (4). They were successfully synthesized from bi-, tri-, and tetratopic phenylamine derivatives (BTPA = bis(4-(1H-1,2,4-triazol-1-yl)phenyl)amine, TTPA = tris(4-incorporating a linear terephthalic acid (H 2 TPA) ligand and Zn(II)/Cd(II) nitrate salts. These transparent crystals present gradually increasing dimensionality and complexity upon extension of the denticity of the phenylamine organic building blocks, as clearly supported by single-crystal X-ray analysis, infrared spectroscopy, elemental analysis, powder X-ray diffraction, and thermogravimetric analysis. Complex 1 shows two-dimensional (2D) threefold-interpenetrating layers (2D + 2D → 2D) with the sql topology that are further formed into a three-dimensional (3D) supramolecular structure by interlayer π•••π stacking and hydrogen-bonding interactions. Complex 2 displays 2D layers with the hcb topology that are further assembled into a 3D fourfold-interpenetrating supramolecular framework with the 3,4,4T25 topology by hydrogen-bonding interactions. Complex 3 possesses a fourfold-interpenetrating 3D (3,4,5)-connected architecture with the 3,4,5T86 topology. Complex 4 features an interesting and unusual new self-penetrating (4,6)-connected 3D topological network with the point symbol of (4 14 • 8)(6 6 ), which contains a fourfold-interpenetrated 3D dia network linked by TPA 2− ligands. The results suggest that these diverse coordination networks mainly can be adjusted by the number of 1,2,4-triazole substituents on the aniline backbones and the coordination geometries of the metal ions. Furthermore, the photoluminescence spectra and emission decay lifetimes of complexes 1−4 were examined.

Assembled synthesis of luminescent mono/double‐layered 2D and 3D Zn (II)‐based coordination polymers tuned by flexible bis (pyridyl)propane‐1,2‐diamines and diverse organic dicarboxylates

“…Meanwhile, the emission maxima of 1–9 present varying degrees of bathochromic shifts in contrast to those of the ligands. The differences in the peak positions of these polymers are closely related to the different coordination environments of Zn (II) cations, diverse conformations of L1 and L2 ligands, or the degree of π‐electron overlap of organic dicarboxylates in their structures . According to the type of dicarboxylates, the luminescent behaviors of these polymers are discussed in the following two groups.…”

Zinc-orotate coordination polymer: synthesis, thermogravimetric analysis and luminescence properties

“…Because of the solidity enhancement of ligand in the complex the fluorescent intensity of 1 is greater than the free ligand. These type of fluorescent performances are carried by an intra ligand (n → π* and π → π*transitions) emission condition that causes the broad emission band of 1 and is having same patterns as in described Zn(II) or metal complexes with O and N-donor ligands having d 10 configuration [41][42][43][44][45][46]. The resemblance among free ligand and emission spectra of complex eradicate the emission intensity, leads to show, luminescent property of the complex which is HOr −2 plated emission.…”

Synthesis, Crystal Structure, and Properties of a New Coordination Polymer Built from N/O-Donor Mixed Ligands

“…The complex 1 shows strong broad photoluminescence emission at 435 nm upon excitation at 359 nm. The intense emission band at 455 nm was observed for a free H2L ligand upon excitation at 342 nm, which may be ascribed to π* → π transition because the conjugative effect of H2L ligand [30].…”

“…The complex 1 shows strong broad photoluminescence emission at 435 nm upon excitation at 359 nm. The intense emission band at 455 nm was observed for a free H 2 L ligand upon excitation at 342 nm, which may be ascribed to π* → π transition because the conjugative effect of H 2 L ligand [30]. However, the H 2 nobda ligand shows weak emission maxima at 420 nm upon excitation at 338 nm, much lower than that of the π-conjugated H 2 L ligand, because the fluorescent emission of the π* → n transition resulting from benzene-dicarboxylate ligands could nearly be neglected in comparison with that arising from the π* → π transition of the π-conjugated H 2 L ligand.…”