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Sains Malaysiana 47(9)(2018): 2083–2090 http://dx.doi.org/10.17576/jsm-2018-4709-16
Synthesis and X-Ray Single Crystal Study of 5-(4,4,5,5 – Tetramethyl – 1,3,2 –Dioxoborolane) – 10,20 – Diphenylporphyrin (Sintesis dan
Kajian Sinar-X
Hablur Tunggal 5-(4,4,5,5-tetrametil-
1,3,2-dioxoborolana)-10,20-difenilporfirin) NUUR
HAZIQAH
MOHD
RADZUAN1,
NAWWAR
HANUN
ABDUL
MALEK1,
MOHAMMAD
FADZLEY
NGATIMAN2,
TAN
KE
XIN3,
MOHD
BAKRI
BAKAR3,
NURUL
IZZATY
HASSAN1
& MUNTAZ
ABU
BAKAR1* 1School of Chemical Sciences
and Food Technology, Faculty of Science and Technology, Universiti
Kebangsaan Malaysia, 43600 UKM Bangi,
Selangor Darul Ehsan, Malaysia 2Centre for Research and
Instrumentation Management, Universiti
Kebangsaan Malaysia, 43600 UKM Bangi,
Selangor Darul Ehsan, Malaysia 3Department of Chemistry,
Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Johor, Johor Bahru, Johor Darul Takzim, Malaysia Diserahkan: 30 Mac 2018/Diterima: 17 Mei 2018 ABSTRACT Borylated porphyrin is one of building blocks in coupling reactions to obtain
the multiporphyrin containing two, three
or more subunits of porphyrins. In this study, one of borylated
porphyrin derivatives, 5-(4,4,5,5 – tetramethyl – 1,3,2 – dioxoborolane)
-10,20 – diphenylporphyrin (B-DPP)
was synthesized through four steps of reactions. The building block
of porphyrin, dipyrromethane was synthesized
through a condensation reaction in the presence of trifluoroacetic
acid as catalyst. Subsequently, A2B2 type of porphyrin was obtained by Lindsey
condensation reaction followed by bromination
reaction to produce porphyrin halide. Suzuki cross coupling reaction
between porphyrin halide and pinacolborane
with Pd (II) catalyst afforded 40% of borylayed porphyrin. The
product was successfully characterized by using nuclear magnetic
resonance spectroscopy (NMR) and UV-Visible spectroscopy (UV-Vis).
This compound crystallized from a mixture of dichloromethane/methanol
to give violet needle-like crystal. Crystallographic studies showed
this compound crystallized in monoclinic system with space group
of P21/c. Keywords: Borylated porphyrin; porphyrin; Suzuki cross coupling; X-ray
structural study ABSTRAK Sebatian porfirin borilasi
merupakan salah
satu blok
binaan dalam
tindak balas penggandingan
untuk mendapatkan
sebatian multiporfirin yang terdiri daripada dua, tiga atau
lebih unit porfirin.
Melalui kajian ini, salah satu
terbitan sebatian
porfirin borilasi, 5-(4,4,5,5-tetrametil-1,3,2-dioxoborolana)-10,20-difenilporfirin
(B-DPP) telah disintesis
melalui empat
langkah tindak balas. Blok binaan
asas iaitu dipirometana disintesis melalui tindak balas penyejatan dengan kehadiran asid trifloroasetik, selaku mangkin. Porfirin jenis A2B2 diperoleh melalui tindak balas penyejatan Lindsey dan diikuti dengan tindak balas pembrominan
untuk menghasilkan
sebatian porfirin halida. Tindak balas penggandingan
Suzuki antara sebatian
porfirin halida dan pinakolborona menggunakan bahan pemangkin Pd (II) menghasilkan 40% sebatian porfirin borilasi. Sebatian ini telah berjaya
dicirikan dengan
menggunakan teknik resonans magnetik nuklear (RMN) dan
spektroskopi ultra-lembayung
boleh nampak
(UL-BN).
Sebatian ini
menghablur daripada sistem campuran pelarut diklorometana/methanol dan menghasilkan kristal jejarum
berwarna ungu.
Kajian kristalografi menunjukkan sebatian ini terhablur
dalam sistem
monoklinik dengan kumpulan ruang P21/c. Kata kunci: Kajian
struktur sinar-X;
porfirin; porfirin borilasi; tindak balas penggandingan Suzuki RUJUKAN Aratani, N., Cho, H.S., Ahn, T.K., Cho, S., Kim, D., Sumi, H. & Osuka, A. 2003. Efficient excitation energy transfer in long
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a 5,15-bisphenylethynylated zn(ii) porphyrin
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Thesis Ph.D. Faculty of Science and Technology, Queensland University
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The Porphyrin Handbooks. San Diego:
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Synthesis of meso-alkenyl monoporphyrins
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porphyrin dyads. SYNLETT 1: 0067-0072. *Pengarang untuk surat-menyurat; email: muntaz@ukm.edu.my
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