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Updated: Oct 11, 2025
Novel Techniques for Observing Structural Dynamics of Photoresponsive Liquid Crystals
Published on: May 29, 2018
Impact of the Structural Modification of Diamondoid Cd(II) MOFs on the Nonlinear Optical Properties
Mayank Gupta1, Ziyu Zhu1, Dileep Kottilil2
1Department of Chemistry, National University of Singapore, Singapore 117543, Singapore.
Abstract:
A change in the degree of interpenetration (DOI) in metal-organic frameworks (MOFs) prompted by heat, pressure, or exchange of solvents is a fascinating phenomenon that can potentially impact the functional properties of MOFs. Structural transformation involving two noncentrosymmetric MOFs with different DOIs provides a rare opportunity to manipulate their optical properties. Herein, we report an unusual single-crystal-to-single-crystal (SCSC) transformation of a noncentrosymmetric 7-fold interpenetrated diamondoid (dia) Cd(II) MOF into another noncentrosymmetric but 8-fold interpenetrated dia MOF upon the removal of guest solvents. A hydrogen-bond network formed between the lattice solvents and linker trans-2-(4-pyridyl)-4-vinylbenzoate (pvb) in a 7-fold interpenetrated noncentrosymmetric MOF results in a significant increase in the two-photon absorption cross-section (11 times) as compared to that in the desolvated 8-fold interpenetrated MOF. Also, an increase in the DOI in the noncentrosymmetric crystals strengthened the π···π interaction between the individual diamondoid networks and enhanced the second-order nonlinear optical (NLO) coefficient (deff) by 4.5 times. These results provide a way to manipulate the optical properties of MOFs using a combined strategy of the formation of hydrogen bonds and interpenetration for access to tunable single-crystal NLO devices in an SCSC manner. By changing the experimental conditions, another dia Cd(II) MOF with 4-fold interpenetration can be isolated. In this centrosymmetric MOF, the olefin groups in the backbone of the ligand (pvb) undergo a [2 + 2] cycloaddition reaction quantitatively under UV light but in a non-SCSC fashion.
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