Sains Malaysiana 55(10)(2026): 1626-1638

http://doi.org/10.17576/jsm-2026-5510-03

 

Synthesis, Characterisation and Density Functional Theory Study of A₄- and A₂B₂- Type Meso-Hexylporphyrin Derivatives and Their Zinc (II) Complexes

(Kajian Teori Fungsian Sintesis, Pencirian dan Ketumpatan bagi Terbitan Meso-Heksilporfirin Jenis A₄- and A₂B₂- serta Kompleks Zink (II)nya)

 

NABILA SYUHADA ZAILAN¹, YASOTHAA A/P RAMAIYAH¹, NUUR HAZIQAH MOHD RADZUAN¹, MOHD BAKRI BAKAR², WAN NURFADHILAH ZAHARIM^1,3 & MUNTAZ ABU BAKAR^1,*

 

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

²Department of Chemical Sciences, Faculty of Science, Universiti Teknologi Malaysia, 81310 UTM Johor Bahru, Johor, Malaysia

³Nuclear Structure Research Group, RIKEN Nishina Center for Accelerator Based Science, 2-1 Hirosawa, Saitama 351-0198, Wako, Japan

 

Received: 21 May 2026/Accepted: 9 September 2026

 

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

 

Abstract

Porphyrin is a macrocylic aromatic compound that has attracted the attention of scientists due to its ability to be tuned for various applications such as photodynamic therapy, catalyst, and DSSC. Understanding the theoretical properties of porphyrin enables electronic tuning for future design, producing efficient functions of porphyrin compounds. An extensive computational study on structural electronic properties of A₄ and A₂B₂ type meso-hexylporphyrin derivatives has yet to be conducted. Therefore, Density Functional Theory method which is a computational study tool was applied in this investigation to study the properties of meso-hexylporphyrin theoretically. In this work, all 4 meso-hexylporphyrin derivatives were synthesised and characterised using Nuclear Magnetic Resonance (NMR) and Ultra Violet-Visible (UV-VIS). Structures were optimized at B3LYP/6-31G(d) and studied based on the structural and electronic properties parameters. From this study, the symmetry and planarity of porphyrin derivatives increase after coordination with the Zn metal complex. Derivatives 1 and 4 were reported to be soft compounds that are more reactive, with a low HOMO-LUMO energy gap, 2.62 eV and 2.74 eV respectively. However, derivatives 3 and 5 are shown as hard compound which are more stable, having a high HOMO-LUMO energy gap, 2.75 eV and 2.91 eV, respectively. This study provides a basis for further exploration of meso-hexylporphyrin as a potential model compound for various applications.

Keywords: DFT study; HOMO-LUMO; macrocyclic aromatic compound; meso-hexylporphyrin

 

Abstrak

Porfirin adalah sebatian aromatik makrosilik yang telah menarik perhatian saintis kerana keupayaannya untuk dioptimumkan kepada pelbagai aplikasi seperti terapi fotodinamik, mangkin dan DSSC. Memahami sifat teori porfirin membolehkan pengubahsuaian elektronik untuk mereka bentuk masa hadapan dan menghasilkan fungsi cekap sebatian porfirin. Kajian pengkomputeran ke atas sifat struktur elektronik mengenai terbitan meso-heksilporfirin jenis A₄ dan A₂B₂ masih belum dijalankan. Oleh itu, kaedah Teori Fungsian Ketumpatan yang merupakan kaedah pengkomputeraan digunakan dalam penyelidikan ini untuk mengkaji sifat terbitan meso-heksilporfirin secara teori. Dalam kajian ini, empat terbitan meso-heksilporfirin telah disintesis dan dicirikan menggunakan analisis Resonans Magnetik Nuklear (RMN) dan Ultra Lembayung Boleh Nampak (ULBN). Struktur telah dioptimumkan pada B3LYP/6-31G(d) dan dikaji berdasarkan parameter sifat struktur dan elektronik. Hasil kajian ini, struktur simetri dan keplanaran terbitan porfirin meningkat selepas pengkoordinatan dengan kompleks logam Zn. Terbitan 1 dan 4 dilaporkan sebagai sebatian lembut yang lebih reaktif tetapi kurang stabil, dengan jurang tenaga HOMO-LUMO yang rendah, masing-masing 2.62 eV dan 2.74 eV. Walau bagaimanapun, terbitan 3 dan 5 ditunjukkan sebagai sebatian keras yang lebih stabil tetapi kurang reaktif, mempunyai jurang tenaga HOMO-LUMO yang tinggi, masing-masing 2.75 eV dan 2.91 eV. Kajian ini menyediakan asas bagi penerokaan lanjut terhadap meso-heksilporfirin sebagai sebatian model yang berpotensi untuk pelbagai aplikasi.

Kata kunci: HOMO-LUMO; kajian DFT; meso-heksilporfirin; sebatian makrosiklik aromatik

 

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