TY - JOUR
T1 - Diversified architectures of one-dimensional zinc(II) and cadmium(II) coordination polymers incorporating bipyridyl ligands
T2 - Syntheses, structures, theoretical studies, fluorescent and nonlinear optical properties
AU - Zhao, Huajian
AU - Jia, Ding
AU - Li, Jianghua
AU - Moxey, Graeme J.
AU - Zhang, Chi
N1 - Publisher Copyright:
© 2015 Published by Elsevier B.V.
PY - 2015/6/1
Y1 - 2015/6/1
N2 - Abstract Reactions of Zn(II)/Cd(II) salts with two bipyridyl ligands afforded four coordination polymers (CPs), [Zn(μ2-4,4′-pytz)(NO2)2]n (1), [Cd(μ2-4,4′-pytz)(μt-4,4′-pytz)(NO2)2]n (2), [Zn(μ2-3,3′-pytz)(NO2)2]n (3), and {[Cd(μ2-3,3′-pytz)1.5(NO2)2]·CH2Cl2}n (4), (4,4′-pytz = 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine, and 3,3′-pytz = 3,6-bis(3-pyridyl)-1,2,4,5-tetrazine). The identities of 1-4 have been unambiguously established by single-crystal X-ray diffraction, and further characterized by Fourier-transform infrared and UV-Vis spectroscopies, elemental analysis, powder X-ray diffraction, electrospray ionization-mass spectrometry (ESI-MS) and fluorescence analysis. CPs 1 and 3 exhibit similar one-dimensional (1-D) zigzag chains containing an octahedral [ZnO4N2] unit bridged by N-donor ligands in the crystal lattice. Among them, 1 and 3 are supramolecular isomers attributing positional isomeric ligands (4,4′-pytz vs 3,3′-pytz). 2 reveals an uncommon 1-D herringbone chain, in which Cd atoms are coordinated by two chelating NO2- ligands and three 4,4′-pytz ligands, one terminal and two bridged, resulting in a pentagonal bipyramid [CdO4N3] structural motif. In 4, the 3,3′-pytz ligands adopt a trans arrangement around the Cd atom, giving a 1-D ladder-like chain structure. Density functional theory and time-dependent density functional theory calculations at the B3LYP/LanL2DZ+6-31G∗ level were performed on compounds 1-3 to rationalize their experimental absorption spectra. The fluorescent properties of the two ligands 4,4′-pytz, 3,3′-pytz, 1-4 and also the mixture with corresponding stoichiometry between the metal salts and ligands of CPs 1-4 have been studied in dimethylformamide (DMF) solutions at room temperature, which revealed that CPs 1-4 exhibit blue emissions. The third-order nonlinear optical (NLO) property of 3 were also investigated.
AB - Abstract Reactions of Zn(II)/Cd(II) salts with two bipyridyl ligands afforded four coordination polymers (CPs), [Zn(μ2-4,4′-pytz)(NO2)2]n (1), [Cd(μ2-4,4′-pytz)(μt-4,4′-pytz)(NO2)2]n (2), [Zn(μ2-3,3′-pytz)(NO2)2]n (3), and {[Cd(μ2-3,3′-pytz)1.5(NO2)2]·CH2Cl2}n (4), (4,4′-pytz = 3,6-bis(4-pyridyl)-1,2,4,5-tetrazine, and 3,3′-pytz = 3,6-bis(3-pyridyl)-1,2,4,5-tetrazine). The identities of 1-4 have been unambiguously established by single-crystal X-ray diffraction, and further characterized by Fourier-transform infrared and UV-Vis spectroscopies, elemental analysis, powder X-ray diffraction, electrospray ionization-mass spectrometry (ESI-MS) and fluorescence analysis. CPs 1 and 3 exhibit similar one-dimensional (1-D) zigzag chains containing an octahedral [ZnO4N2] unit bridged by N-donor ligands in the crystal lattice. Among them, 1 and 3 are supramolecular isomers attributing positional isomeric ligands (4,4′-pytz vs 3,3′-pytz). 2 reveals an uncommon 1-D herringbone chain, in which Cd atoms are coordinated by two chelating NO2- ligands and three 4,4′-pytz ligands, one terminal and two bridged, resulting in a pentagonal bipyramid [CdO4N3] structural motif. In 4, the 3,3′-pytz ligands adopt a trans arrangement around the Cd atom, giving a 1-D ladder-like chain structure. Density functional theory and time-dependent density functional theory calculations at the B3LYP/LanL2DZ+6-31G∗ level were performed on compounds 1-3 to rationalize their experimental absorption spectra. The fluorescent properties of the two ligands 4,4′-pytz, 3,3′-pytz, 1-4 and also the mixture with corresponding stoichiometry between the metal salts and ligands of CPs 1-4 have been studied in dimethylformamide (DMF) solutions at room temperature, which revealed that CPs 1-4 exhibit blue emissions. The third-order nonlinear optical (NLO) property of 3 were also investigated.
KW - Fluorescent
KW - Herringbone chain
KW - Nonlinear optics
KW - TD-DFT
KW - Zinc and cadmium coordination polymers
UR - http://www.scopus.com/inward/record.url?scp=84926430601&partnerID=8YFLogxK
U2 - 10.1016/j.ica.2015.03.025
DO - 10.1016/j.ica.2015.03.025
M3 - Article
SN - 0020-1693
VL - 432
SP - 1
EP - 12
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
M1 - 16475
ER -