Cadmium(II)-Organic Frameworks with the Polynuclear Unit: Dimensionality Control and Luminescence Response to Pyridine

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Abstract

New porous metal-organic frameworks (MOF) [Cd7(Btdc)7(Bpa)2(Dmf)2(H2O)2] · 15Dmf · 2H2O (I) and [Cd7(Btdc)7(Bpe)2(Dmf)2] · 15Dmf · 3H2O (II) (H2Btdc is 2,2’-bithiophene-5,5’-dicarboxylic acid, Bpa is 1,2-bis(4-pyridyl)ethane, Bpe is 1,2-bis(4-pyridyl)ethylene, and Dmf is N,N-dimethylformamide) are synthesized under solvatothermal conditions. The structures and compositions of the compounds are determined by single-crystal X-ray diffraction (XRD) (CIF files ССDС nos. 2364290 (I) and 2364289 (II)) and confirmed by powder XRD, elemental analysis, thermogravimetry, and IR spectroscopy. Compound I has a 2D structure based on the heptanuclear discrete building unit {Cd7} with the linear structure. Compound II is a 3D MOF in which the {Cd7} building units are linked into a continuous chain motif due to additional interactions. The formation of discrete or continuous chains is directly related to the nature of the N-donor bridging ligand (Bpe or Bpa). Compounds I and II have open structures with the accessible volume about 50%. The solvate molecules are replaced by thiophene, benzene, and pyridine, and the luminescence properties of the prepared adducts are studied. Luminescence quenching in the presence of thiophene and an increase in the luminescence intensity in the presence of pyridine accompanied by a change in the quantum yield by 4–5 times are shown.

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About the authors

V. A. Dubskikh

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Email: dan@niic.nsc.ru
Russian Federation, Novosibirsk

A. A. Lysova

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Email: dan@niic.nsc.ru
Russian Federation, Novosibirsk

D. G. Samsonenko

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Email: dan@niic.nsc.ru
Russian Federation, Novosibirsk

D. N. Dybtsev

Nikolaev Institute of Inorganic Chemistry, Siberian Branch, Russian Academy of Sciences

Author for correspondence.
Email: dan@niic.nsc.ru
Russian Federation, Novosibirsk

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2. Fig. 1. Structure of coordination polymer I: structure of the secondary building block (a); projection of the three-dimensional coordination polymer in different directions (b-d); view of the packing of layers along the crystallographic axis a (e). Hydrogen atoms and guest solvent molecules are not shown for clarity.

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3. Fig. 2. Structure of coordination polymer II: structure of the secondary building block (a); projection of the two-dimensional coordination polymer in different directions (b-d). Hydrogen atoms and guest solvent molecules are not shown for clarity.

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4. Fig. 3. Comparison of experimental (red) and theoretical (black) powder diffractograms for compounds I (a) and II (b).

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5. Fig. 4. Thermogravimetric curves for compounds I (red) and II (black).

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6. Fig. 5. Photoluminescence emission spectra of compounds I (a) and II (b) for samples: freshly synthesized (black) and aged in thiophene (green), benzene (red), pyridine (blue).

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