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

    Authors

    L. Croitor; E. B. Coropceanu; A. E. Masunov; H. J. Rivera-Jacquez; A. V. Siminel;M. S. Fonari

    Comments

    Authors: contact us about adding a copy of your work at STARS@ucf.edu

    Abbreviated Journal Title

    J. Phys. Chem. C

    Keywords

    DENSITY-FUNCTIONAL THEORY; 2-PHOTON ABSORPTION PROPERTIES; METAL-ORGANIC; FRAMEWORK; COORDINATION POLYMERS; TD-DFT; STRUCTURAL-CHARACTERIZATION; LUMINESCENT PROPERTIES; FLEXIBLE LIGAND; EXCITED-STATES; MOLECULES; Chemistry, Physical; Nanoscience & Nanotechnology; Materials Science, ; Multidisciplinary

    Abstract

    Interaction of zinc(II) and cadmium(II) sulfates with pyridine-4-aldoxime (4-pyao) and pyridine-4amidoxime (4-pyamo) ligands resulted in four 1D metalorganic 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(10, A = 4-pyamo for 3, M = Cd(II), A = 4-pyamo for 4, and mononuclear [Zn(SO4)(4-pyamo)(2)(H2O)(3)] S. 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 1-3 have been also evaluated. The solid-state emission of 1D polymers 1-3 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-organic nonlinear optical materials.

    Journal Title

    Journal of Physical Chemistry C

    Volume

    118

    Issue/Number

    17

    Publication Date

    1-1-2014

    Document Type

    Article

    Language

    English

    First Page

    9217

    Last Page

    9227

    WOS Identifier

    WOS:000335433100058

    ISSN

    1932-7447

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