Sains Malaysiana 47(4)(2018): 741-747

http://dx.doi.org/10.17576/jsm-2018-4704-12

Structural and Optical Properties Investigation on H-Bonded 1D Helical Self Assembly of 1,1-Dibenzyl-3-(2-Bromobenzoyl)thiourea Molecules for Nonlinear Optical Application

(Kajian Struktur dan Sifat Optik Himpunan Kendiri Molekul 1,1-Dibenzil-3-(2- Bromobenzoil)thiourea dengan Ikatan-H 1D untuk Aplikasi Optik tak Linear)

WUN FUI MARK-LEE¹, MOHD FAIZAL MD NASIR² & MOHAMMAD B. KASSIM¹*

¹School of Chemical Sciences and Food Technology, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan, Malaysia

²Fuel Cell Institute, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor Darul Ehsan, Malaysia

Received:  16 September 2017/Accepted: 11 November 2017

ABSTRACT

A benzoylthiourea molecule namely 1,1-dibenzyl-3-(2-bromobenzoyl)thiourea (2BrBT) was synthesized and characterized by C, H, N and S elemental, mass spectrometry and spectroscopic analyses (infrared, ultraviolet-visible and nuclear magnetic resonance). The 2BrBT compound crystallized in a tetragonal system with the space group P4₃ and exhibits an acentric crystalline packing due to the presence of intermolecular H-bonding network that forms a self-assembly of 1D helical motif. The asymmetric delocalisation of electrons in the molecule retains its transparency throughout the visible and near-infrared region and hence, essentially propagates the macroscopic helical motif in the solid state. The highest-occupied and lowest-unoccupied molecular orbital (HOMO/LUMO) are mainly found on the thiourea moiety and the benzoylthiourea fragment, respectively and shows an optical bandgap of 3.50 eV. The influence of its geometrical characteristics to the optical properties of 2BrBT is established and discussed in view of nonlinear optical (NLO) application.

Keywords: Benzoylthiourea; crystal structure; DFT; nonlinear optical material

ABSTRAK

Molekul benzoiltiourea terbitan 1,1-dibenzil-3-(2-bromobenzoil)tiourea (2BrBT) telah berjaya disintesis dan dicirikan menggunakan teknik analisis unsur C, H, N dan S, spektrometri jisim dan spektroskopi (FT-IR, UV-Vis, ¹H dan ¹³C NMR). Kompaun 2BrBT menghablur dalam sistem tetragonal dengan kumpulan ruang P4₃ dan menunjukkan padatan hablur yang bersifat asentrik akibat jaringan ikatan-H 1D. Jaringan akibat ikatan hidrogen intermolekul menyebabkan molekul 2BrBT tersusun secara kendiri untuk membentuk motif heliks satu dimensi dalam keadaan fasa pepejal. Penyahsetempatan elektron secara asimetrik di dalam molekul telah mengekalkan sifat lutsinar terhadap radiasi di seluruh kawasan cahaya nampak dan inframerah-dekat serta menggalakkan pembentukan motif makroskopik heliks dalam keadaan pepejal. Pengaruh geometri terhadap sifat optik molekul 2BrBT dibincang dan dihubungkaitkan terhadap aplikasi optik tak linear (NLO).

Kata kunci: Bahan optik tak linear; benzoil tiourea; struktur kristal; teori fungsi ketumpatan (DFT)

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*Corresponding author; email: mb_kassim@ukm.edu.my