Density Functional Study of Metal-to-Ligand Charge Transfer and Hole-Hopping in Ruthenium(II) Complexes with Alkyl-Substituted Bipyridine Ligands

Salmahaminati,; Abe, Masahide; Purnama, Indra; Mulyana, Jacob Yan; Hada, Masahiko

doi:10.1021/acsomega.0c01199

Cited by 15 publications

(9 citation statements)

References 52 publications

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“…Pendekatan ini mampu mendapatkan hasil yang akurat pada skala mikroskopik dan telah dikonfirmasi dengan hasil eksperimental. Metode DFT merupakan metode Ab Initio (Salmahaminati et al, 2021) sehingga dapat menentukan konformasi struktur senyawa yang paling stabil, dan nilai parameter seperti sifat fisika dan kimia yang dihasilkan lebih akurat dari semi empiris. Dari latar belakang tersebut perlunya dilakukan pengkajian secara komputasi melalui metode HF (Nurcahyo et al, 2017) dan DFT yang penelitian sebelumnya telah dianalisis oleh Salmahaminati dan Fajar (2015) untuk mengetahui apakah dapat senyawa EPMS dapat dimanfaatkan sebagai bahan tabir surya dan penerapannya pada pembuatan losion tabir surya.…”

Section: Gambar 1 Senyawa Kimia Empsunclassified

“…Langkah pertama pembuatan struktur senyawa EPMS di AVOGADRO (Snyder & Kucukkal, 2021) dan dilakukan dengan meminimisasi struktur dengan menjalankan optimasi geometri terhadap senyawa EPMS hasil dari langkah pertama yang menggunakan GaussView versi 5.0 sebagai viewer input sebelum perhitungan menggunakan Gaussian versi 0.9W (Frisch et al, 2009) and for Windows. Optimasi geometri dilakukan dengan menggunakan metode HF (Hartree Fock) serta Basis set (Schuchardt et al, 2007;Hehre et al, 1972;Feller, 1996) 6-31G (Purnama et al, 2019;Salmahaminati et al, 2021) sehingga struktur dengan energi paling rendah mampu dihasilkan. Analisis spektrum menggunakan TD-DFT (Fumanal & Daniel, 2016).…”

Section: Metode Komputasiunclassified

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Chemical predictive modeling of ethyl-p-methoxycinnamate and synthesis of natural lotion from kencur (Kaempferia galanga L.) as sunscreen agents

Salmahaminati

Fitri²,

Kusuma³

2023

J. Ilm. Pertan.

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Solar radiation is essential for the evolution of life on earth. Solar radiation, including ultraviolet radiation (UV), reaches the earth's surface. The sun emits three types of UV radiation: UVA, UVB, and UVC, which have beneficial and harmful effects on the human body. The most important benefit is the synthesis of vitamin D in the skin. However, UVB radiation also causes direct photochemical damage to DNA. This study aimed to investigate the ability of the compound ethyl-p-methoxycinnamate (EPMS) that is available in kencur as a sunscreen agent through computational chemistry studies using the Hartree-Fock (HF) method and time-dependent density functional theory (TD-DFT) and perform synthesis of lotion from kencur extract. The investigation began with creating a molecular model of a sunscreen agent optimized for geometry using the HF method and continued with spectrum analysis using TD-DFT. The study's results showed that the analysis of the EPMS spectrum could be used as a natural UVB shield. In addition, the synthesis of lotion from kencur rhizome made using oil and water phases showed organoleptic, pH, homogeneity, and spreadability test results fitted according to the Indonesian National Standard (SNI) 16-4399-1996. It indicated that kencur lotion could potentially be used as a sunscreen agent.

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Section: Gambar 1 Senyawa Kimia Empsunclassified

Section: Metode Komputasiunclassified

Chemical predictive modeling of ethyl-p-methoxycinnamate and synthesis of natural lotion from kencur (Kaempferia galanga L.) as sunscreen agents

Salmahaminati

Fitri²,

Kusuma³

2023

J. Ilm. Pertan.

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“…Recent theoretical calculation indicates that the reorganization energy is regulated by the order of alkyl chains. The reorganization energy decreases as the order of the alkyl chains increases . In addition, the reorganization energy has a good linear relationship with the reciprocal of the conjugated unit of thiophene ring (1/ n thiophene ) (see Table S2).…”

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confidence: 93%

Conformational Order of Alkyl Side Chain of Poly(3-alkylthiophene) Promotes Hole-Extraction Ability in Perovskite/Poly(3-alkylthiophene) Heterojunction

Zhu

Lai

et al. 2021

J. Phys. Chem. Lett.

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Molecular structures of hole transport materials (HTMs) have significant impact on the optoelectronic properties of perovskite/HTM heterojunction. But the structure–property relationship in the heterojunction remains poorly understood. By using poly(3-alkylthiophene) (P3AT) as the HTM model, here we apply sum frequency generation vibrational spectroscopy to establish correlations among conformations of P3ATs, the hole extraction ability of P3ATs from the perovskite layer, and the charge mobility of P3ATs. It is revealed that with similar energy-level alignment, the conformational order of alkyl side chains in regioregular P3ATs can effectively regulate the hole extraction ability of P3ATs from perovskite layer by tuning reorganization energy. By contrast, the charge mobility of P3ATs strongly depends on the P3AT backbone’s coplanarity. Our findings decouple the roles of the long-hidden conformational order of alkyl side chain and the polythiophene backbone’s coplanarity on the performance of perovskite/HTM heterojunction, offering useful guidelines for boosting the performance of optoelectronic devices.

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“…Over the last few decades, photocatalysis has been intensively studied for polymer synthesis with visible light. − Ir and Ru complexes have been widely used as photosensitizers because of their outstanding visible light absorption and long excited-state lifetimes. − The combinations of the photosensitizer of the Ir(III) or Ru(II) complex and the reactive center of the Pd(II) complex may provide effective dinuclear catalysts for photopolymerization. Murata et al reported that the dinuclear Ru–Pd catalyst [Ru(bpy) 2 (bpm Br )PdMe(Me 2 CO)] 3+ (Figure a, Ru–Pd0 ; bpy = 2,2′-bipyridine, bpm Br = 5,5′-dibromo-2,2′-bipyrimidine) was active for the dimerization of α-methylstyrene (AMS) using light irradiation.…”

Section: Introductionmentioning

confidence: 99%

Density Functional Study on the Photopolymerization of Styrene Using Dinuclear Ru–Pd and Ir–Pd Complexes with Naphthyl-Substituted Ligands

et al. 2023

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A density functional study was performed to investigate the mechanism of the photocatalytic reactivity of styrene polymerization using dinuclear Ru–Pd and Ir–Pd catalytic complexes. In previous experiments with these catalysts, the reactivity increased, and more polymer products were yielded compared to dimers under visible light irradiation. The best catalytic reactivity was obtained using an Ir–Pd complex containing naphthyl substituents at the phenyl ligands coordinated to Ir (Ir–Pd1). In contrast, Ir–Pd2, an isomer of Ir–Pd1, containing naphthyl substituents at the pyridine ligands, did not show good reactivity, which may be related to the stability of the excited state of the catalytic complexes. In this study, we calculated the radiative lifetimes of these catalytic complexes and Ir–Pd1 had the longest lifetime; this result was consistent with the experimental results. The longest lifetime of the Ir–Pd1 was attributed to the destabilization of the highest occupied molecular orbital (HOMO) energy by π*−π* interactions between the naphthyl and phenyl ligands. Further, this destabilization of the HOMO energy afforded a small energy gap between the HOMO and lowest unoccupied molecular orbital, enhancing the metal-to-ligand charge transfer to the bridging ligand between Ir and Pd. Additionally, we focused on the reaction of the second insertion of styrene, which was identified as the rate-determining step of the polymerization cycle in a previous study. The singlet–triplet crossing points of the intermediates were estimated, and the barrier heights of the intersystem crossing were much lower than those in the thermal paths, which explained the efficiency of the photocatalytic reactivity in the experiment.

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Density Functional Study of Metal-to-Ligand Charge Transfer and Hole-Hopping in Ruthenium(II) Complexes with Alkyl-Substituted Bipyridine Ligands

Cited by 15 publications

References 52 publications

Chemical predictive modeling of ethyl-p-methoxycinnamate and synthesis of natural lotion from kencur (Kaempferia galanga L.) as sunscreen agents

Chemical predictive modeling of ethyl-p-methoxycinnamate and synthesis of natural lotion from kencur (Kaempferia galanga L.) as sunscreen agents

Conformational Order of Alkyl Side Chain of Poly(3-alkylthiophene) Promotes Hole-Extraction Ability in Perovskite/Poly(3-alkylthiophene) Heterojunction

Density Functional Study on the Photopolymerization of Styrene Using Dinuclear Ru–Pd and Ir–Pd Complexes with Naphthyl-Substituted Ligands

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