Study of Substituent Effect on Properties of Platinum(II) Porphyrin Semiconductor Using Density Functional Theory

Harno Dwi Pranowo; Fadjar Mulya; Hafiz Aji Aziz; Grisani Ambar Santoso

doi:10.22146/ijc.26121

Study of Substituent Effect on Properties of Platinum(II) Porphyrin Semiconductor Using Density Functional Theory

https://doi.org/10.22146/ijc.26121

Harno Dwi Pranowo^(1*), Fadjar Mulya⁽²⁾, Hafiz Aji Aziz⁽³⁾, Grisani Ambar Santoso⁽⁴⁾

(1) Austrian-Indonesian Centre for Computational Chemistry, Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta, 55281, Indonesia
(2) Austrian-Indonesian Centre for Computational Chemistry, Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta, 55281, Indonesia
(3) Austrian-Indonesian Centre for Computational Chemistry, Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta, 55281, Indonesia
(4) Austrian-Indonesian Centre for Computational Chemistry, Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Gadjah Mada, Sekip Utara, Yogyakarta, 55281, Indonesia
(*) Corresponding Author

Abstract

Study of substituent effect on properties of platinum(II) porphyrin had been performed using DFT method. The aim of the study is to investigate the effect of substituent group on the electronic and optical properties of the platinum(II) porphyrin. Geometry optimization was conducted using DFT/B3LYP/LANL2DZ to obtain molecular structure, electronic structure and energy profile. Band gap energy (E_g), the density of states (DOS), and UV-visible spectra are the semiconductor parameters to study. Computational results show that platinum(II) porphyrin and substituted platinum(II) porphyrin have properties of semiconductor based on E_g value, DOS, and UV-visible spectra. The results show that Mulliken partial charges of electron withdrawing substituents are higher than the electron donating substituents (CH₃, OH, and NH₂). E_g values of the complexes with respect to the substituents follow this order: NH₂ < OH < NO₂ < COOH < I < CH₃ < Br < F < H, for DOS_HOMO values, the order is CH₃ < NO₂ < I < OH < F < NH₂ < COOH < Br < H and the maximum wavelength (λ_max) for UV-visible adsorption spectra follows this order: NH₂ > OH > COOH > NO₂ > I > Br > CH₃ > F > H. Molecules with smaller E_g and DOS_HOMO values and higher λ_max are considered as the most appropriate semiconductor materials. Our results show that Pt(II)P-NH₂ has the smallest E_g and the highest λ_max among other substituted platinum(II) porphyrin molecules. Therefore, Pt(II)P-NH₂ are the most suitable semiconductor material based on the aforementioned criteria.

Keywords

platinum(II) porphyrin; semiconductor; substituent effect

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DOI: https://doi.org/10.22146/ijc.26121