Malaysian Journal of Analytical Sciences Vol 21 No 1 (2017): 60 - 71

DOI: http://dx.doi.org/10.17576/mjas-2017-2101-08

 

 

 

SYNTHESIS AND STRUCTURAL CHARACTERIZATION OF

N-BROMOBENZOYL-N'-(1,10-PHENANTHROLIN-5-YL)THIOUREA DERIVATIVES

 

(Sintesis dan Penentuan Struktur Ligan Terbitan N-Bromobenzoil-N'-(1,10-Fenantrolin-5-il) tiourea)

 

Rosidah Shardin¹, Siew San Tan¹, Mohammad B. Kassim^1,2*

 

¹School of Chemical Sciences and Food Technology, Faculty of Science and Technology

²Fuel Cell Institute

Universiti Kebangsaan Malaysia, 43600 UKM Bangi, Selangor, Malaysia

 

*Corresponding author: mb_kassim@ukm.edu.my

 

 

Received: 28 September 2016; Accepted: 8 December 2016

 

 

Abstract

Derivatives of N-bromobenzoyl-N'-(1,10-phenanthrolin-5-yl)thiourea were successfully synthesized from the reaction of 1,10-phenanthroline with x-bromobenzoylisothiocyanate (x = ortho, meta and para) to give phen-o-BrBT, phen-m-BrBT and phen-p-BrBT, respectively. The molecular structures of the derivatives compounds were elucidated based on the crystal structure of N-bromobenzoyl-N'-(1,10-phenanthrolin-5-yl)thiourea, CHNS elemental analysis, mass spectrometry, spectroscopic data (infrared, ultraviolet-visible, nuclear magnetic resonance and luminescence) and cyclic voltammetry.The mass spectrum show similar m/z values at 460.9 and 260.0, which represent the molecular ions for [(phen-x-BrBT)-Na]⁺ and [BrBT]⁺, respectively. The presence of a v(NH) (3389-3599 cm^-1) and the disappearance of ν(NH₂) bands from 1,10-phenanthroline-5-amine indicate the formation of the N-bromobenzoyl-N'-(1,10-phenanthrolin-5-yl)thiourea. Attachment of a Br atom to the benzoyl moiety reduced the stretching frequency of C=O group by >20 cm^-1 compared with phen-BT ligand. The compounds exhibit two π→π* bands at 231 and 269-270 nm for the phenanthroline and benzoyl moieties, respectively. The resonance for N-H proton appeared at δ = 11.53-12.49 ppm. In addition, ¹³C resonance signals for C=S and C=O groups were recorded at around 182 and 167.39-169.08 ppm, respectively. The synthesis and effect of a Br substitution on the structural and luminescence properties of N-bromobenzoyl-N'-(1,10-phenanthrolin-5-yl)thiourea derivatives are presented and discussed in this study.

 

Keywords:  benzoylthiourea, 1,10-phenanthroline, thiocyanate, infrared, luminescence

 

Abstrak

Terbitan N-bromobenzoil-N'-(1,10-fenantrolin-5-il)tiourea telah disintesis melalui tindak balas di antara 1,10-fenantrolina dengan x-bromobenzoilisotiosianat (x = orto, meta and para) masing-masing menghasilkan sebatian phen-o-BrBT, phen-m-BrBT dan phen-p-BrBT. Struktur sebatian ditentukan berdasarkan struktur kristal N-benzoil-N'-(1,10-fenantrolin-5-il)tiourea, analisis unsur CHNS, spektrometri jisim, data spektroskopi (inframerah, ultralembayung-boleh nampak, pendarcahaya dan resonans magnetik nuklear) dan voltammetri kitaran. Spektrum jisim bagi ketiga-tiga sebatian ini menunjukkan nilai m/z yang sama pada 460.9 dan 260.0 masing-masing mewakili ion molekul [(phen-x-BrBT)-Na]⁺ dan [BrBT]⁺. Kemunculan isyarat v(NH) pada 3389-3599 cm^-1 dan kehilangan frekuensi regangan ν(NH₂) bagi sebatian 1,10-fenantrolin-5-amina menunjukkan pembentukan molekul N-bromobenzoil-N'-(1,10-fenantrolin-5-il)tiourea. Kehadiran atom bromo pada gelang benzoil telah merendahkan frekuensi regangan v(CO) sebanyak >20 cm^-1 berbanding N-bromobenzoil-N'-(1,10-fenantrolin-5-il)tiourea. Spektrum elektronik sebatian memapar dua jalur serapan bagi peralihan π→π* pada 231 dan 269-270 nm masing-masing berpunca daripada moieti fenantrolina dan benzoil. Isyarat resonan ¹H (N-H) hadir pada δ = 11.53-12.49 ppm manakala, isyarat ¹³C bagi kumpulan berfungsi utama C=S dan C=O telah dikenal pasti masing-masing pada 182 dan 167.39-169.08 ppm. Sintesis dan kesan kehadiran Br pada posisi orto, meta dan para terhadap struktur serta sifat pendarcahaya sebatian dilapor dan dibincang di dalam kajian ini.

 

Kata kunci:  benzoilthiourea, 1,10-fenantrolina, tiosianat, inframerah, pendarcahaya

 

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