Solvent Influence in Obtaining Diverse Coordination Symmetries of Dy(III) Metal Centers in Coordination Polymers: Synthesis, Characterization, and Luminescent Properties

Abstract

Six new Dy(III)-containing coordination polymers (CPs) have been synthesized emphasizing the role of solvent molecules in directing the formation of the Dy(III) coordination sphere which in turn influences the dimensionality of the coordination polymer, thermal stability, and emission properties. An isophthalate-based flexible ligand 5-[(anthracen-9-ylmethyl)amino]-isophthalic acid (H 2 L) with different solvents such as dimethylformamide (DMF), dimethylacetamide (DMA), dimethyl sulfoxide (DMSO), diethylformamide (DEF), and N-donor linkers phen (1,10-phenanothroline) and pyridine (py) was employed to o b t a i n s i x d i ff e r e n t c o o r d i n a t i o n p o l y m e r s , 5), and [Dy(L)(NO 3 )(py) 2 •py] n (6), respectively. All the compounds were characterized by IR spectroscopy and thermogravimetric analysis, and unambiguously characterized by single crystal X-ray crystallography. The bulky anthracenyl group of the linker H 2 L in combination with the solvent molecules significantly alters the coordination symmetry of the Dy(III) coordination sphere in the polymers in the manner: D 2d in 1, C 2v and D 4d in 2, C 4v and C s in 3, C 5v in 4, D 4d in 5, and D 2d in 6. The coordination symmetry plays an interesting role in sensitization of lanthanide emission. The emission maxima of compounds 1−6 vary from the blue region to the yellow region significantly due to coordination symmetry expressed by the Dy(III) centers, which in turn depends upon the coordinated solvent molecule. The thermogravimetric profile indicates the thermal stability of the solvent free compounds up to 300 °C.

Advances in 2D coordination networks for single‐crystal‐to‐single‐crystal applications beyond confined pores

“…An important conceptual characteristic of such 2D frameworks is a possibility of guest‐induced stretching and sliding between layer and layer via tuning of weak interactions such as van der Waals interactions, ion‐dipole forces, hydrogen bondings, and dipole–dipole attractions 15–20 . For 2D networks, the interlayer sliding and stretching phenomena are strongly depending on the hydrophilicity, coordinating ability, protic properties, polarity, and bulkiness of adsorbed guest molecules 21–26 . For example, some pliable 2D coordination systems have been known to be able to provide polymorphism that are sensitive to various conditions 27–33 .…”

“…[15][16][17][18][19][20] For 2D networks, the interlayer sliding and stretching phenomena are strongly depending on the hydrophilicity, coordinating ability, protic properties, polarity, and bulkiness of adsorbed guest molecules. [21][22][23][24][25][26] For example, some pliable 2D coordination systems have been known to be able to provide polymorphism that are sensitive to various conditions. [27][28][29][30][31][32][33] Furthermore, recent publications on single crystals consisting of 2D frameworks demonstrate that dynamic and structural transformation occurs via modulation of interlayer interactions in single-crystal-to-singlecrystal (SCSC) mode.…”

Cadmium-Inspired Self-Polymerization of {LnIIICd2} Units: Structure, Magnetic and Photoluminescent Properties of Novel Trimethylacetate 1D-Polymers (Ln = Sm, Eu, Tb, Dy, Ho, Er, Yb)

“…Such properties may include a combination of non-trivial magnetism and luminescence [ 4 , 5 ] or conductivity [ 6 , 7 , 8 ], a combination of magnetism and rotation of polarized light [ 9 , 10 ], sensitivity of magnetic properties to irradiation [ 11 ], or thermochromic properties [ 12 ], electrochromism [ 13 ], the ability to convert mechanic deformation into voltage and vice versa [ 14 ] to display thermoelectric behavior [ 15 ] or magnetocaloric effect [ 16 ]. A change in the physical properties of a compound in comparison with the known prototype can be achieved by fine-tuning its structure by changing the synthesis conditions [ 17 ] or by an irreversible post-synthetic reaction [ 18 , 19 ], while a reversible change in the property can be caused by interaction with a certain substrate [ 20 ].…”

New High-Nuclear Coordination Complexes Constructed by 2-Hydroxymethylpyridine: From Antiferromagnetic to Spin Glass and Ferromagnetic Behavior

“…High-nuclear metal coordination complexes, constructed by organic ligands and metal ions/clusters, − have attracted a great deal of interest due to their novel structures and unique properties, especially molecular magnetism. − The structures of coordination complexes may be affected by a variety of experimental factors such as reaction temperature, , pH, , organic ligands, and solvents. − If we can manage appropriate organic ligands and metal ions/clusters with specific functions in a preconceived way by controlling the reaction conditions, new complexes with expected structures and magnetic properties will be obtained . Current reports indicate that the magnetic properties of the materials can be influenced not only by the intramolecular structures but also by the intermolecular interactions such as π–π stacking or hydrogen bonding. − These intermolecular interactions could construct a short-range array of spins between clusters and affect the behavior of magnetism, , which may be an effective approach to adjust the magnetism.…”