Interplay of bipyridine and 4,4′-diaminodiphenylmethane ligands in crystal design of cadmium-based coordination polymers: Structures and unusual photoluminescence quenching
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CRACIUN, Nicoleta Irina, MELNIK, E., KULIKOVA, Olga, SIMINEL, Anatolii, CHIŞCA, Diana, FONARI, Marina. Interplay of bipyridine and 4,4′-diaminodiphenylmethane ligands in crystal design of cadmium-based coordination polymers: Structures and unusual photoluminescence quenching. In: Polyhedron, 2024, vol. 251, p. 0. ISSN 0277-5387. DOI: https://doi.org/10.1016/j.poly.2024.116850
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Polyhedron
Volumul 251 / 2024 / ISSN 0277-5387 /ISSNe 1873-3719

Interplay of bipyridine and 4,4′-diaminodiphenylmethane ligands in crystal design of cadmium-based coordination polymers: Structures and unusual photoluminescence quenching

DOI:https://doi.org/10.1016/j.poly.2024.116850

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Craciun Nicoleta Irina1, Melnik E.1, Kulikova Olga1, Siminel Anatolii1, Chişca Diana2, Fonari Marina1
 
1 Institute of Applied Physics, MSU,
2 "Ion Creangă" State Pedagogical University from Chisinau
 
 
Disponibil în IBN: 24 februarie 2024


Rezumat

Starting from Cd(ClO4)2·2H2O, four positively charged coordination polymers were prepared and characterized by IR spectroscopic and single-crystal X-ray diffraction methods. The obtained crystalline solids included one-dimensional coordination polymers, {[Cd(dadpm)(2,2′-bpy)2](ClO4)2}n (1), and {[Cd(dadpm)(2,2′-bpy)2](ClO4)2·0.5(H2O)}n (2), and two-dimensional coordination polymers, {[Cd(4,4′-bpy)2(H2O)2](ClO4)2(dadpm)2}n (3), and {[Cd(4,4′-bpy)2(H2O)2](ClO4)2(4,4′-bpy)0.5(dadpm)·EtOH}n (4) (dadpm = 4,4′-diaminodiphenylmethane, 2,2′-bpy = 2,2′-bipyridine; 4,4′-bpy = 4,4′-bipyridine). The similar one-dimensional coordination backbones in 1 and 2 were originated from the mononuclear Cd(II) coordination cores with the N6 distorted octahedral geometries going from two terminal bidentate-chelate 2,2′-bpy and two bidentate-bridging dadpm ligands that mediated the successive metal atoms in coordination chains. The charge-balanced perchlorate anions were located in the interchain space complemented by water molecules in 2. The coordination chains were interconnected into H-bonded networks via NH(NH2)⋯O hydrogen bonds. The 2D coordination polymers 3 and 4 comprised the same positively charged square-grid infinite networks {[Cd(4,4′-bpy)2(H2O)2]2+}n with sql topology and with cadmium atom in the N4O2 tetragonally distorted octahedral coordination geometry as a single node. The charge-compensated ClO4 anions and the dadpm molecules were located in the interlayer space in 3 being complemented by the 4,4′-bpy and EtOH molecules in 4. The solid-state photoluminescence in all reported coordination polymers was significantly attenuated and redistributed along the spectrum in comparison with the pure dadpm which revealed the dual emission in the form of a strong narrow signal in the ultraviolet and a weak signal in the yellow regions of spectrum.

Cuvinte-cheie
4, 4′-Diaminodiphenylmethane, cadmium, IR spectroscopy, photoluminescence, X-ray

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<cfAbstr cfLangCode='EN' cfTrans='o'><p>Starting from Cd(ClO<sub>4</sub>)<sub>2</sub>&middot;2H<sub>2</sub>O, four positively charged coordination polymers were prepared and characterized by IR spectroscopic and single-crystal X-ray diffraction methods. The obtained crystalline solids included one-dimensional coordination polymers, {[Cd(dadpm)(2,2&prime;-bpy)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>}<sub>n</sub>&nbsp;(1), and {[Cd(dadpm)(2,2&prime;-bpy)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>&middot;0.5(H<sub>2</sub>O)}<sub>n</sub>&nbsp;(2), and two-dimensional coordination polymers, {[Cd(4,4&prime;-bpy)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>(dadpm)<sub>2</sub>}<sub>n</sub>&nbsp;(3), and {[Cd(4,4&prime;-bpy)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>](ClO<sub>4</sub>)<sub>2</sub>(4,4&prime;-bpy)<sub>0.5</sub>(dadpm)&middot;EtOH}<sub>n</sub>&nbsp;(4) (dadpm = 4,4&prime;-diaminodiphenylmethane, 2,2&prime;-bpy = 2,2&prime;-bipyridine; 4,4&prime;-bpy = 4,4&prime;-bipyridine). The similar one-dimensional coordination backbones in 1 and 2 were originated from the mononuclear Cd(II) coordination cores with the N<sub>6</sub>&nbsp;distorted octahedral geometries going from two terminal bidentate-chelate 2,2&prime;-bpy and two bidentate-bridging dadpm ligands that mediated the successive metal atoms in coordination chains. The charge-balanced perchlorate anions were located in the interchain space complemented by water molecules in 2. The coordination chains were interconnected into H-bonded networks via NH(NH<sub>2</sub>)⋯O hydrogen bonds. The 2D coordination polymers 3 and 4 comprised the same positively charged square-grid infinite networks {[Cd(4,4&prime;-bpy)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]<sup>2+</sup>}<sub>n</sub>&nbsp;with sql topology and with cadmium atom in the N<sub>4</sub>O<sub>2</sub>&nbsp;tetragonally distorted octahedral coordination geometry as a single node. The charge-compensated ClO<sub>4</sub><sup>&minus;</sup>&nbsp;anions and the dadpm molecules were located in the interlayer space in 3 being complemented by the 4,4&prime;-bpy and EtOH molecules in 4. The solid-state photoluminescence in all reported coordination polymers was significantly attenuated and redistributed along the spectrum in comparison with the pure dadpm which revealed the dual emission in the form of a strong narrow signal in the ultraviolet and a weak signal in the yellow regions of spectrum.</p></cfAbstr>
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