| Project/Area Number |
22H00325
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| Research Category |
Grant-in-Aid for Scientific Research (A)
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| Allocation Type | Single-year Grants |
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| Section | 一般 |
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| Review Section |
Medium-sized Section 34:Inorganic/coordination chemistry, analytical chemistry, and related fields
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| Research Institution | Nara Institute of Science and Technology |
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Principal Investigator |
ラッペン ゲナエル 奈良先端科学技術大学院大学, 先端科学技術研究科, 教授 (60812576)
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| Co-Investigator(Kenkyū-buntansha) |
川井 茂樹 国立研究開発法人物質・材料研究機構, マテリアル基盤研究センター, グループリーダー (30716395)
西野 智雄 奈良先端科学技術大学院大学, 先端科学技術研究科, 助教 (60824878)
安原 主馬 奈良先端科学技術大学院大学, 先端科学技術研究科, 准教授 (90545716)
服部 陽平 奈良先端科学技術大学院大学, 先端科学技術研究科, 特任助教 (30843271)
尾本 賢一郎 奈良先端科学技術大学院大学, 先端科学技術研究科, 特任助教 (40820056)
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| Project Period (FY) |
2022-04-01 – 2027-03-31
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| Project Status |
Granted (Fiscal Year 2024)
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| Budget Amount *help |
¥41,860,000 (Direct Cost: ¥32,200,000、Indirect Cost: ¥9,660,000)
Fiscal Year 2025: ¥8,190,000 (Direct Cost: ¥6,300,000、Indirect Cost: ¥1,890,000)
Fiscal Year 2024: ¥8,970,000 (Direct Cost: ¥6,900,000、Indirect Cost: ¥2,070,000)
Fiscal Year 2023: ¥11,050,000 (Direct Cost: ¥8,500,000、Indirect Cost: ¥2,550,000)
Fiscal Year 2022: ¥9,100,000 (Direct Cost: ¥7,000,000、Indirect Cost: ¥2,100,000)
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| Keywords | Molecular gears / Ruthenium complexes / Lanthanide complexes / Aromatic compounds / STM / Molecular machines / Double-decker complexes / Molecular gear / Single molecule / Tripodal ligand |
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| Outline of Research at the Start |
Exploitation of machines at the single molecular level is the ultimate miniaturization for the emergence of radically new technologies in the field of nanomedicine, sustainable development and energy harvesting. Molecular design, chemical synthesis and STM experiments will be combined to investigate the mechanical properties of rotating molecular machines. Our goal is to push molecular machines from the flask to the real world with prototypes of winches and gears. Transfer of rotation in a train of gears will be achieved and the laws governing the mechanics of such movements established.
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| Outline of Annual Research Achievements |
First, the STM manipulations of the ruthenium-based molecular gear prototypes synthesized in the last year were explored. Unfortunately, they were not successful, despite our previous studies with similar anchoring ligands (Pentabrominated pentaphenylcyclopentadienyl ligand), the new complexes with the extended tripodal rotative units are not able to be correctly deposited. They were found on their side which render them unable to be used as gears.
In this year, we also continued to work on the synthesis of the proposed molecular gears. Only one new type of gear was finished, the double-decker complexes of cerium(IV) coordinated to a thioether functionalized phthalocyanine anchoring ligand and a helical naphthalocyanine rotating cogwheel functionalized with four carbazoles acting as teeth. This structure is very promising for STM studies.
We also started to study by STM the nano-winch successfully synthesized with a family of loads (fullerenes, triptycenes, and porphyrins) but the study is not conclusive yet.
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| Current Status of Research Progress |
Current Status of Research Progress
2: Research has progressed on the whole more than it was originally planned.
Reason
The research is going smoothly with the main part of this project, the synthesis of the molecular gear targets which started in different complimentary directions.
Concerning the manpower, a new specially appointed assistant professor on the project has been enrolled (Dr. Hattori Yohei). He will be involved in the supervision of a new Master student on the topic.
A collaboration with a theoretician (Dr. J. Cuny from the University of Toulouse, France) will be pursued to modelize the intermolecular interactions in a train of molecular gears and evaluate the energy barrier of such transfer of rotation.
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| Strategy for Future Research Activity |
For the coming year, we will work on the synthesis of our next synthetic targets, the molecular gears prototypes with the very innovative, but challenging, cycloheptatriene and cyclooctatetraene ligands as cogwheels. We plan to use the free ligand as gears but also their corresponding ruthenium(II) or Cerium (IV) complexes to alleviate them from the surface. Both strategies will be exploredby STM so free aromatic ligands as well as their comlexes are required.This new type of gears are aiming to improve the propagation efficiency of their gear motion with an unprecedented number of teeth of 7 and 8.
In addition to the synthetic work, we are also working on the STM manipulations of a family of cyclopentadiene derivatives and the new double-decker complexes of cerium(IV) coordinated to a thioether functionalized phthalocyanine anchoring ligand and a helical naphthalocyanine rotating cogwheel functionalized with four carbazoles acting as teeth. This structure is very promising for their manipulation as a train of gear. We target to follow the transfer of rotation from one molecule to the next with the aim of transferring this rotation to more than 3 molecules, which is still up to now our best result.
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