Sains Malaysiana 53(8)(2024): 1937-1952

http://doi.org/10.17576/jsm-2024-5308-17

Microwave vs. Reflux Synthesis of Bis-Thiourea Derivative: Yield Optimization, Crystallographic Understanding and Optical Sensing Potential

(Sintesis Gelombang Mikro lawan Refluks Terbitan Bis-Tiourea: Pengoptimuman Hasil, Pemahaman Kristalografi dan Potensi Penderiaan Optik)

HASANAIN SALAH NAEEM^1,2, ISRAA JABER², SUHAILA SAPARI¹, FAZIRA ILYANA ABDUL RAZAK⁴, BILAL MAJID RUDAINI⁵, NURUL HIDAYAH ABD RAZAK¹, ASMAA. SOHEIL. NAJM³ & SITI AISHAH HASBULLAH^1,*

¹Department of Chemical Sciences, Faculty of Science and Technology, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia

²Faculty of Pharmacy, University of Al Muthanna, Samawah 66001, Iraq

³Department of Electrical, Electronics and System, FKAB, Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia

⁴Department of Chemistry, Faculty of Science, Universiti Teknologi Malaysia, 81310 Johor Bahru, Johor, Malaysia

⁵Department of Pharmacy, Al-Maarif University College, Al Anbar,31001, Iraq

Received: 4 December 2023/Accepted: 13 June 2024

Abstract

A new bis-thiourea (BT) derivative was successfully synthesized using both conventional reflux and microwave irradiation methods. The microwave irradiation reaction yielded a greater percentage yield of 73%, while the reflux heating yielded only 44%. The microwave irradiation procedure takes a minimum of 10 min to complete, in contrast to the reflux heating method, which takes 24 h. The compound was characterised using a variety of spectroscopic techniques, including UV-Vis, FTIR, nuclear magnetic resonance (¹H-NMR and ¹³C-NMR), and single crystal X-ray crystallography (XRC). It shows that BT has a high ability to form hydrogen bonds of both intermolecular and intramolecular types, as demonstrated by X-ray crystallography and DFT calculations. In addition, this research provides insights into the possible uses of BT in coordination chemistry involving metal ions, such as a copper ions. Through the use of density-functional theory (DFT) and UV-Vis investigations, it is envisaged that the BT compound has a strong tendency to form stable copper ion complexes. This is supported by the optimal energy value E(UB3LYP) observed for the Cu(II) complex.

Keywords: Bis-thiourea derivative; DFT optimization; microwave reaction; single crystal

Abstrak

Dalam penyelidikan ini, sebatian bis-tiourea, BT telah berjaya disintesis menggunakan kaedah konvensional (refluks) dan kaedah penyinaran mikrogelombang. Kaedah penyinaran mikrogelombang memberikan peratusan hasil yang tinggi iaitu 73%, manakala kaedah refluks memberikan hanya 44%. Kaedah penyinaran mikrogelombang memerlukan masa hanya 10 minit untuk selesai berbanding dengan kaedah refluks memerlukan masa sehingga 24 jam. Pencirian struktur sebatian dijalankan menggunakan pelbagai kaedah spektroskopi iaitu spektroskopi ultra lembayung - boleh nampak (ULBN), spektroskopi Fourier transformasi inframerah (FTIR), spektroskopi resonans magnetik nukleus ¹H dan ¹³C (¹H-RMN dan ¹³C-RMN) dan kristalografi sinar-X hablur tunggal (X-Ray). Berdasarkan daripada kajian X-ray dan kajian teori fungsi ketumpatan (DFT), sebatian BT mempunyai keupayaan yang tinggi membentuk ikatan hidrogen secara intramolekul dan intermolekul. Lebih-lebih lagi, kajian ini memberikan penggunaan sebatian BT dalam kimia pengikatan melibatkan ion logam seperti ion kuprum. Melalui kajian fungsi ketumpatan (DFT) dan pemerhatian ULBN, sebatian BT berupaya membentuk kompleks ion kuprum yang stabil. Ini disokong oleh oleh pemerhatian ke atas kompleks Cu(II) melalui nilai tenaga optimum E(UB3LYP).

Kata kunci: Hablur tunggal; pengoptimuman DFT; terbitan bis-tiourea; tindak balas sinaran mikrogelombang

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*Corresponding author; email: aishah80@ukm.edu.my