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Gyroscope Like Metal Complexes

类陀螺仪金属配合物

基本信息

批准号：
1900549
负责人：
John Gladysz
金额：
$ 48.5万
依托单位：
Texas A&M University
依托单位国家：
美国
项目类别：
Standard Grant
财政年份：
2019
资助国家：
美国
起止时间：
2019-08-15 至 2024-07-31
项目状态：
已结题

来源：
https://www.nsf.gov/awardsearch/showAward?AWD_ID=1900549&HistoricalAwards=false
关键词：
Gyroscope Like Metal Complexes

项目摘要

The Chemical Synthesis Program of the Chemistry Division of the National Science Foundation supports the research led by Professor John Gladysz of Texas A & M University. The project focuses on the design and synthesis of molecules that act as gyroscopes. These compounds have potential applications for sensors and guidance devices. Like classic mechanical gyroscopes - a device consisting of a wheel or disk mounted so that it can spin rapidly about an axis, the new molecules have a rigid axis composed of phosphorus-metal-phosphorus bonds and flexible linking groups connected to the polar phosphorus atoms that may rotate about the axis. This project aims to create molecules that both resemble mechanical gyroscopes and reproduce their functions. This research is important as it demonstrates complex design and synthesis protocols that may enable new molecular machines to be constructed. This project provides broad training for undergraduate, graduate student, and postdoctoral coworkers, as well as high school students and teachers. The team acquires expertise in synthesis, characterization techniques, oral presentation skills, report writing, laboratory safety, data management, and working in teams that are diverse with respect to gender, ethnicity, and nationality. Results are disseminated in the peer-reviewed scientific literature (including open access media), in lectures to undergraduate groups, at "open houses" for the lay public, and at diverse meetings and conferences.This project focuses on the synthesis, fundamental structural and dynamic properties, and reactivity of gyroscope-like metal-based molecular rotors. These molecular gyroscopes feature a metal fragment encased in a cage-like trans-dibridgehead diphosphine ligand in which the phosphorus atoms are spanned by three hydrocarbon chains. If the ligands are sufficiently small relative the linkages, the metal units rotate within the cage. Arrays of gyroscope-like units with parallel axes can be synthesized with spacings that allow the rotators to interact, enforcing correlated motion such as in gearboxes. The metal fragments also can be removed, providing new classes of macrocyclic dibridgehead diphosphines. These ligands are able to turn themselves "inside out", and be applied as container molecules that transport precious metals from one aqueous phase to another, leaving base metals behind.This award reflects NSF's statutory mission and has been deemed worthy of support through evaluation using the Foundation's intellectual merit and broader impacts review criteria.

美国国家科学基金会化学部的化学合成计划支持德克萨斯州A M大学的John Gladysz教授领导的研究。该项目的重点是设计和合成的分子，作为陀螺仪。这些化合物在传感器和制导装置方面具有潜在的应用价值。就像经典的机械陀螺仪-一种由轮子或圆盘组成的装置，它可以绕轴快速旋转，新分子有一个由磷-金属-磷键组成的刚性轴和连接到极性磷原子的柔性连接基团，这些磷原子可以绕轴旋转。该项目旨在创造既类似于机械陀螺仪又能再现其功能的分子。这项研究很重要，因为它展示了复杂的设计和合成协议，可以使新的分子机器被构建。该项目为本科生、研究生和博士后同事以及高中学生和教师提供广泛的培训。该团队获得了合成，表征技术，口头陈述技能，报告撰写，实验室安全，数据管理以及在性别，种族和国籍方面多样化的团队中工作的专业知识。研究结果通过同行评审的科学文献（包括开放获取媒体）、大学生讲座、面向公众的“开放日”以及各种会议和研讨会进行传播。该项目侧重于陀螺仪式金属基分子转子的合成、基本结构和动力学特性以及反应性。这些分子陀螺仪的特点是金属碎片包裹在笼状的反式双桥头双膦配体中，其中磷原子由三个烃链跨越。如果配体相对于键足够小，则金属单元在笼内旋转。具有平行轴的类似陀螺仪的单元阵列可以与允许旋转器相互作用的间距合成，从而实现相关运动，例如在齿轮箱中。也可以除去金属碎片，提供新类别的大环二桥头二膦。这些配体能够将自己“由内而外”，并作为容器分子应用，将贵金属从一个水相运输到另一个水相，而将贱金属留在后面。该奖项反映了NSF的法定使命，并通过使用该基金会的智力价值和更广泛的影响审查标准进行评估，被认为值得支持。

项目成果

期刊论文数量（13）

专著数量（0）

科研奖励数量（0）

会议论文数量（0）

专利数量（0）

A surprise landing on the terra incognita of macrocyclic dibridgehead diorganoarsines: syntheses, structures, and reactivities

意外登陆大环二桥头二有机胂的未知领域：合成、结构和反应性

DOI：
10.1039/d2cc03235j
发表时间：
2022
期刊：
Chemical Communications
影响因子：
4.9
作者：
Zarcone, Samuel R.;Verardi, Peter J.;Bhuvanesh, Nattamai;Gladysz, John A.
通讯作者：
Gladysz, John A.

Building Blocks for Molecular Polygons Based on Platinum Vertices and Polyynediyl Edges

基于铂顶点和聚炔二基边的分子多边形构建块

DOI：
10.1021/acs.organomet.2c00573
发表时间：
2023
期刊：
Organometallics
影响因子：
2.8
作者：
Collins, Brenna K.;Weisbach, Nancy;Hampel, Frank;Bhuvanesh, Nattamai;Gladysz, John A.
通讯作者：
Gladysz, John A.

Platinum( ii ) alkyl complexes of chelating dibridgehead diphosphines P((CH 2 ) n ) 3 P ( n = 14, 18, 22); facile cis / trans isomerizations interconverting gyroscope and parachute like adducts

螯合双桥头二膦 P((CH 2 ) n ) 3 P ( n = 14, 18, 22) 的铂( ii )烷基络合物；

DOI：
10.1039/d1dt02321g
发表时间：
2021
期刊：
Dalton Transactions
影响因子：
4
作者：
Zhu, Yun;Ehnbom, Andreas;Fiedler, Tobias;Shu, Yi;Bhuvanesh, Nattamai;Hall, Michael B.;Gladysz, John A.
通讯作者：
Gladysz, John A.

Macrocyclic Complexes Derived from Four cis ‐L 2 Pt Corners and Four Butadiynediyl Linkers; Syntheses, Electronic Structures, and Square versus Skew Rhombus Geometries

由四个顺式 -L 2 Pt 角和四个丁二炔二基连接体衍生的大环配合物；

DOI：
10.1002/chem.202100305
发表时间：
2021
期刊：
Chemistry – A European Journal
影响因子：
0
作者：
Collins, Brenna K.;Clough Mastry, Melissa;Ehnbom, Andreas;Bhuvanesh, Nattamai;Hall, Michael B.;Gladysz, John A.
通讯作者：
Gladysz, John A.

Toward Frameworks with Multiple Aligned and Interactive Fe(CO) 3 Rotators: Syntheses and Structures of Diiron Complexes Linked by Two trans -Diaxial α,ω-Diphosphine Ligands Ar 2 P(CH 2 ) n PAr 2

具有多个对齐和相互作用的 Fe(CO) 3 旋转体的框架：由两个反式双轴α,β-二膦配体 Ar 2 P(CH 2 ) n PAr 2 连接的狄铁配合物的合成和结构

DOI：
10.1021/acs.inorgchem.0c03737
发表时间：
2021
期刊：
Inorganic Chemistry
影响因子：
4.6
作者：
Zarcone, Samuel R.;Chu, Gong M.;Ehnbom, Andreas;Cardenal, Ashley;Fiedler, Tobias;Bhuvanesh, Nattamai;Hall, Michael B.;Gladysz, John A.
通讯作者：
Gladysz, John A.