Effect of molecular packing of zinc(II) porphyrins on the performance of field-effect transistors

Hoang, Mai Ha; Ngo, Trinh Tung; Nguyen, Duc Nghia

doi:10.1088/2043-6262/5/4/045012

Cited by 8 publications

(6 citation statements)

References 18 publications

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“…Insights can be extracted from crystal structure data of Y3 (CCDC deposit no. 1912230), as shown in Figure in relation to typical interactions observed in porphyrin-based crystal structures. , As indicated in Figure a, the closest distance between two Y3 molecules is about 6.0 Å. This is much longer than between molecules characterized by π–π stacking, which usually show closest molecule–molecule distances between 3.4 and 3.6 Å .…”

Section: Resultsmentioning

confidence: 91%

The Central Role of Ligand Conjugation for Properties of Coordination Complexes as Hole-Transport Materials in Perovskite Solar Cells

Zhang

Hua

Wang

et al. 2019

ACS Appl. Energy Mater.

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Two zinc-based coordination complexes Y3 and Y4 have been synthesized and characterized, and their performance as hole-transport materials (HTMs) for perovskite solar cells (PSCs) has been investigated. The complex Y3 contains two separate ligands, and the molecular structure can be seen as a disconnected porphyrin ring. On the other hand, Y4 consists of a porphyrin core and therefore is a more extended conjugated system as compared to Y3. The optical and redox properties of the two different molecular complexes are comparable. However, the hole mobility and conductivity of Y4 as macroscopic material are remarkably higher than that of Y3. Furthermore, when employed as hole-transport materials in perovskite solar cells, cells containing Y4 show a power conversion efficiency (PCE) of 16.05%, comparable to the Spiro-OMeTAD-based solar cells with an efficiency around 17.08%. In contrast, solar cells based on Y3 show a negligible efficiency of about 0.01%. The difference in performance of Y3 and Y4 is analyzed and can be attributed to the difference in packing of the nonplanar and planar building blocks in the corresponding materials.

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Section: Resultsmentioning

confidence: 91%

The Central Role of Ligand Conjugation for Properties of Coordination Complexes as Hole-Transport Materials in Perovskite Solar Cells

Zhang

Hua

Wang

et al. 2019

ACS Appl. Energy Mater.

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“…The degree of molecular ordering and packing can impact various solid‐state properties of TPMs, including their charge transport properties [64,65] . DFT calculations revealed that the molecular geometry is significantly affected by the nature of the metal.…”

Section: Resultsmentioning

confidence: 99%

Molecular Engineering of Metalloporphyrins for High‐Performance Energy Storage: Central Metal Matters

et al. 2023

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Porphyrin derivatives represent an emerging class of redox‐active materials for sustainable electrochemical energy storage. However, their structure–performance relationship is poorly understood, which confines their rational design and thus limits access to their full potential. To gain such understanding, we here focus on the role of the metal ion within porphyrin molecules. The A2B2‐type porphyrin 5,15‐bis(ethynyl)‐10,20‐diphenylporphyrin and its first‐row transition metal complexes from Co to Zn are used as models to investigate the relationships between structure and electrochemical performance. It turned out that the choice of central metal atom has a profound influence on the practical voltage window and discharge capacity. The results of DFT calculations suggest that the choice of central metal atom triggers the degree of planarity of the porphyrin. Single crystal diffraction studies illustrate the consequences on the intramolecular rearrangement and packing of metalloporphyrins. Besides the direct effect of the metal choice on the undesired solubility, efficient packing and crystallinity are found to dictate the rate capability and the ion diffusion along with the porosity. Such findings open up a vast space of compositions and morphologies to accelerate the practical application of resource‐friendly cathode materials to satisfy the rapidly increasing need for efficient electrical energy storage.

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“…A much less-explored type of NFA is hybrid organic/inorganic coordination compounds, where the coordination with a main group element or transition metal provides an additional way to tune properties such as the molecular shape, crystallinity, and optoelectronic properties. Examples in the literature of coordination complexes specifically explored for organic photovoltaic applications include porphyrins and phthalocynanines, − which are planar with a strong tendency to π-stack; boron dipyrromethenes (BODIPY) and boron azadipyrromethenes (aza-BODIPY), − which are also planar conjugated molecules better known for their outstanding optical properties; and subphthalocyanines, which are umbrella-shaped conjugated molecules. , …”

Section: Introductionmentioning

confidence: 99%

Monofluorination of Naphthyls Promotes the Cofacial π–π Stacking and Increases the Electron Mobility of Non-Planar Zinc(II) Complexes of Di(naphthylethynyl)azadipyrromethene

et al. 2022

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The homoleptic zinc(II) complex of [2,8-di(1naphthylethynyl) 3,7-diphenyl 1,9-(4-hexylphenyl)azadipyrromethene (ZnL2) 2 ] is a promising non-planar nonfullerene acceptor for organic photovoltaic applications, but it has a relatively low electron mobility that may limit its performance. Here, we explored the fluorination of peripheral aryl groups to increase intermolecular cofacial π−π stacking interactions, which are desirable for electron transport. Complexes with fluorine on the distal phenyls [Zn(1F-L2) 2 ], on the naphthyls [Zn(2F-L2) 2 ], and on both [Zn(3F-L2) 2 ] were synthesized and characterized. All three complexes had similar optical and electrochemical properties. The crystal packing structure of Zn(2F-L2) 2 and Zn(3F-L2) 2 revealed cofacial parallel-displaced π−π stacking between the fluorinated 1-naphthylethynyl groups. Such a cofacial orientation was not observed in Zn(L2) 2 crystals, suggesting that fluorination of the naphthyl groups promotes the cofacial π−π stacking orientation. The hole mobility increased from 1.0 × 10 −4 cm 2 V −1 s −1 for Zn(L2) 2 to 0.8−1.0 × 10 −3 cm 2 V −1 s −1 for the fluorinated complexes. Fluorination on the naphthyl groups increased the electron mobility from 4.2 × 10 −5 cm 2 V −1 s −1 for Zn(L2) 2 and Zn(1F-L2) 2 to 2.0 × 10 −4 cm 2 V −1 s −1 for Zn(2F-L2) 2 and Zn(3F-L2) 2 , consistent with cofacial π−π stacking being favorable for electron transport. The three complexes were tested in OPVs using regioregular poly(3-hexylthiophene) (P3HT) as the p-type material, and the best power conversion efficiencies were 5.2, 5.4, and 5.8% for Zn(2F-L2) 2 , Zn(1F-L2) 2 , and Zn(3F-L2) 2 , respectively, compared to 5.5% for Zn(L2) 2 . The fluorination combination found in Zn(3F-L2) 2 resulted in the best device performance. This study points to a viable strategy to increase the electron mobility and performance of non-planar zinc(II) complexes of azadipyrromethene.

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Effect of molecular packing of zinc(II) porphyrins on the performance of field-effect transistors

Cited by 8 publications

References 18 publications

The Central Role of Ligand Conjugation for Properties of Coordination Complexes as Hole-Transport Materials in Perovskite Solar Cells

The Central Role of Ligand Conjugation for Properties of Coordination Complexes as Hole-Transport Materials in Perovskite Solar Cells

Molecular Engineering of Metalloporphyrins for High‐Performance Energy Storage: Central Metal Matters

Monofluorination of Naphthyls Promotes the Cofacial π–π Stacking and Increases the Electron Mobility of Non-Planar Zinc(II) Complexes of Di(naphthylethynyl)azadipyrromethene

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