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Functionalized organic frameworks explored as second order NLO agents

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Abstract

A new class of chiral phthalimides functionalized with aryl piperazines was designed anticipating their strong candidature for crystal engineering and technological applications. Five new phthalimides were synthesized, characterized and subjected to single crystal X-ray diffraction study that directed their non-centrosymmetric structures. Four phthalimides crystallized in P21 space group with monoclinic crystal system, however, one was found to possess P212121 space group with orthorhombic system. The supramolecular architectures of phthalimide crystals were analysed by an approach based on consideration of energy of intermolecular interaction. The molecular hyperpolarizability (β) calculation for all the listed phthalimides indicated their promising candidature for NLO materials. Further, the crystalline form of all phthalimides was evaluated for their second harmonic generation (SHG) response. A significant response of 16.4 mV was measured for phthalimide possessing t-butyl substituent at the para position of 4-benzylpiperazine. This high SHG response may be attributed to the molecular chirality and helical supramolecular frameworks stabilized by C-H ⋯O hydrogen bonds in the solid state. The current study attests chiral phthalimides possessing arylpiperazines as effective nominees to the area of crystal engineering and nonlinear optics.

New chiral phthalimides possessing terminal arylpiperazines have been studied for their solid-state properties. The second order NLO response of all the listed phthalimides was substantiated with the aid of computational study and crystal engineering approach.

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Acknowledgements

BR is grateful to the Department of Science and Technology, Ministry of Science and Technology, India for financial support (SR/FT/CS-108/2010). Scientific collaboration was possible due to India-Ukraine Bilateral Scientific Cooperation program supported by Department of Science and Technology, Ministry of Science & Technology, India and The Ukrainian State Agency for Science, Innovation, and Informatization (0114U003690). We are thankful to Dr. Svetlana V. Shishkina for her valuable corrections. AKS and VB are thankful to CSIR, India for providing Senior Research Fellowship.

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Authors and Affiliations

  1. Bio-organic Research Laboratory, Department of Chemistry, University of Delhi, Delhi, 110 007, India

    ANIL K SINGH, VIJAY BAHADUR & BRAJENDRA K SINGH

  2. Department of Chemistry, Hansraj College, University of Delhi, Delhi, 110 007, India

    BRIJESH RATHI & TARUNA SINGH

  3. State Scientific Institution “Institute for Single Crystals”, National Academy of Science of Ukraine, 60 Leninaave, Kharkiv, 61001, Ukraine

    VOLODYMYR V MEDVIEDIEV, OLEG V SHISHKIN & NIKOLAY YU GOROBETS

  4. CSIR-National Physical Laboratory, Dr. K S Krishnan Road, New Delhi, 110 012, India

    N VIJAYAN

  5. PG& Research Department of Physics, Arignar Anna Government Arts College, Musiri, 621 211, India

    V BALACHANDRAN

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  1. ANIL K SINGH
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Correspondence to BRIJESH RATHI.

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Supplementary Information

All additional information relating to characterization of the compounds such as NMR spectras (Figures S1–S15), TGA-DTA plots (Figures S16–S20), UV-Vis spectra (Figure S21), supramolecular architecture of crystals presented as packing of molecules and hedgehogs of intermolecular interactions (Figures S23–S27), Crystallographic data (Table S1), Geometrical parameters of intermolecular interactions in crystals (Table S2) and Numbering of dimers, symmetry operation of second molecule of dimer and energy of intermolecular interactions in dimers formed by the basic molecule in the crystals (Tables S3–S7) are given in the supporting information available at www.ias.ac.in/chemsci.

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SINGH, A.K., RATHI, B., MEDVIEDIEV, V.V. et al. Functionalized organic frameworks explored as second order NLO agents. J Chem Sci 128, 297–309 (2016). https://doi.org/10.1007/s12039-015-1012-x

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