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Neutral mononuclear, dinuclear, tetranuclear d7/d10 metal complexes containing bis-pyrazole/pyridine ligands supported by 2,6-bis(3-pyrazolyl)pyridine: synthesis, structure, spectra, and catalytic activity.

Journal Article


Abstract


  • A series of novel bis-pyrazole/pyridine complexes, [Zn(2)(HL(1))(2)(��(2)-SO(4))](2)��EtOH��H(2)O (1), [Co(2)(HL(1))(2)(��(2)-SO(4))](2)��2DMF��6H(2)O (2), [Zn(4)(HL(1))(4)(��(4)-SO(4))][OH](2) (3), [Zn(2)(HL(2))(2)(��(2)-SO(4))]��2H(2)O (4), [Zn(H(2)L(2))(H(2)O)(2)](SO(4))��0.87H(2)O (5) (H(2)L(1) = 2,6-di-(5-phenyl-1H-pyrazol-3-yl)pyridine, H(2)L(2) = 2,6-di-(5-methyl-1H-pyrazol-3-yl)pyridine), were synthesized hydrothermally from the self-assembly of Zn(II) or Co(II) with different types of bipyrazolyl/pyridine derivative ligands. All the complexes were characterized by elemental analysis, IR and UV-vis spectroscopy, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction. Structural analyses revealed that metal atoms (Zn and Co) in complexes 1-5 are five-coordination modes, forming slightly distorted trigonal bipyramidal geometries. In complexes 1-3, H(2)L(1) ligand connected the two metal centers via the tetradentate fashion, and the same form of connection was found in complex 4 with H(2)L(2) ligand. While in complex 5, H(2)L(2) only connected with one metal center via the tridentate fashion, which was different from those in complexes 1-4. Additionally, there are abundant hydrogen bonding interactions in complexes 1-4. Interestingly, for hydrogen bonding connecting fashions being different, the molecules for the complexes 1 and 4 are held together by the hydrogen bond to form a 1D supramolecular structure, whereas complexes 2 and 3 are a hydrogen bonded dimer. In addition, quantum chemical calculations for 1, 3, and 4, thermal behaviors and photoluminescent properties for 1 and 3-5 were performed and discussed in detail. In the mean time, we found that these complexes had potential catalytic activity for the oxidation reaction of cyclohexane.

UOW Authors


  •   Li, Zhen (external author)

Publication Date


  • 2012

Citation


  • Wan, L., Zhang, C., Xing, Y., Li, Z., Xing, N., Wan, L., & Shan, H. (2012). Neutral mononuclear, dinuclear, tetranuclear d7/d10 metal complexes containing bis-pyrazole/pyridine ligands supported by 2,6-bis(3-pyrazolyl)pyridine: synthesis, structure, spectra, and catalytic activity.. Inorganic chemistry, 51(12), 6517-6528. doi:10.1021/ic202678s

Web Of Science Accession Number


Start Page


  • 6517

End Page


  • 6528

Volume


  • 51

Issue


  • 12

Place Of Publication


Abstract


  • A series of novel bis-pyrazole/pyridine complexes, [Zn(2)(HL(1))(2)(��(2)-SO(4))](2)��EtOH��H(2)O (1), [Co(2)(HL(1))(2)(��(2)-SO(4))](2)��2DMF��6H(2)O (2), [Zn(4)(HL(1))(4)(��(4)-SO(4))][OH](2) (3), [Zn(2)(HL(2))(2)(��(2)-SO(4))]��2H(2)O (4), [Zn(H(2)L(2))(H(2)O)(2)](SO(4))��0.87H(2)O (5) (H(2)L(1) = 2,6-di-(5-phenyl-1H-pyrazol-3-yl)pyridine, H(2)L(2) = 2,6-di-(5-methyl-1H-pyrazol-3-yl)pyridine), were synthesized hydrothermally from the self-assembly of Zn(II) or Co(II) with different types of bipyrazolyl/pyridine derivative ligands. All the complexes were characterized by elemental analysis, IR and UV-vis spectroscopy, powder X-ray diffraction (PXRD), and single-crystal X-ray diffraction. Structural analyses revealed that metal atoms (Zn and Co) in complexes 1-5 are five-coordination modes, forming slightly distorted trigonal bipyramidal geometries. In complexes 1-3, H(2)L(1) ligand connected the two metal centers via the tetradentate fashion, and the same form of connection was found in complex 4 with H(2)L(2) ligand. While in complex 5, H(2)L(2) only connected with one metal center via the tridentate fashion, which was different from those in complexes 1-4. Additionally, there are abundant hydrogen bonding interactions in complexes 1-4. Interestingly, for hydrogen bonding connecting fashions being different, the molecules for the complexes 1 and 4 are held together by the hydrogen bond to form a 1D supramolecular structure, whereas complexes 2 and 3 are a hydrogen bonded dimer. In addition, quantum chemical calculations for 1, 3, and 4, thermal behaviors and photoluminescent properties for 1 and 3-5 were performed and discussed in detail. In the mean time, we found that these complexes had potential catalytic activity for the oxidation reaction of cyclohexane.

UOW Authors


  •   Li, Zhen (external author)

Publication Date


  • 2012

Citation


  • Wan, L., Zhang, C., Xing, Y., Li, Z., Xing, N., Wan, L., & Shan, H. (2012). Neutral mononuclear, dinuclear, tetranuclear d7/d10 metal complexes containing bis-pyrazole/pyridine ligands supported by 2,6-bis(3-pyrazolyl)pyridine: synthesis, structure, spectra, and catalytic activity.. Inorganic chemistry, 51(12), 6517-6528. doi:10.1021/ic202678s

Web Of Science Accession Number


Start Page


  • 6517

End Page


  • 6528

Volume


  • 51

Issue


  • 12

Place Of Publication