Mechanism of Nonlinear Optical Enhancement and Supramolecular Isomerism in 1D Polymeric Zn(II) and Cd(II) Sulfates with Pyridine-4-aldoxime Ligands

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• 作者：Lilia Croitor ; Eduard B. Coropceanu ; Art毛m E. Masunov ; Hector J. Rivera-Jacquez ; Anatolii V. Siminel ; Marina S. Fonari
• 刊名：Journal of Physical Chemistry C
• 出版年：2014
• 出版时间：May 1, 2014
• 年：2014
• 卷：118
• 期：17
• 页码：9217-9227
• 全文大小：524K
• 年卷期：v.118,no.17(May 1, 2014)
• ISSN：1932-7455

文摘

Interaction of zinc(II) and cadmium(II) sulfates with pyridine-4-aldoxime (4-pyao) and pyridine-4-amidoxime (4-pyamo) ligands resulted in four 1D metal鈥搊rganic materials (MOMs) with identical composition, [M(SO₄)A₂(H₂O)₂]_n, where M = Zn(II), A = 4-pyao for 1, M = Cd(II), A = 4-pyao for 2, M = Zn(II), A = 4-pyamo for 3, M = Cd(II), A = 4-pyamo for 4, and mononuclear [Zn(SO₄)(4-pyamo)₂(H₂O)₃] 5. New coordination polymers represent the mixed-ligand supramolecular isomers different by the twisting of two pyridine-4-oxime ligands in the metal coordination environments, and crystallizing in the different space groups. Conformational preferences and nonlinear optical properties of the 4-pyao and 4-pyamo complexes were investigated using density functional theory. Spectral properties of 1鈥?b>3 have been also evaluated. The solid-state emission of 1D polymers 1鈥?b>3 appears to be ligand-based, as the positions of the emission maxima remain practically unchanged from free ligand to complexes. The enhancement of luminescence and two-photon absorption in polymers in comparison with the pure ligands is attributed to the chelation of the ligand to the metal center. The detailed mechanism of this enhancement upon complex formation is analyzed and can be used in future design of metal鈥搊rganic nonlinear optical materials.