Harnessing the Reactivity of Sulfur: From Novel S-Atom Transfer Reagents to Sulfide-Protected Nanoclusters

在化学系化学合成项目的支持下，加州大学圣巴巴拉分校的特雷弗·海顿教授将探索含硫金属络合物的化学。硫磺在工业、医药和生物中起着关键作用。支撑这种化学反应的很大一部分是金属硫化物的反应性。在这个项目中，海顿教授将开发金属硫化物的几种新应用，包括一氧化氮传递、有机合成中催化硫原子转移和量子计算。这项研究将为本科生和研究生提供空气敏感金属络合物的合成和表征方面的出色培训，为他们在学术界、工业界和国家实验室系统的职业生涯做好准备。此外，海顿教授将开发一个由学生主导的虚拟研讨会系列，向学生介绍尖端纳米科学。这一系列课程将特别允许本科生与来自其他机构的研究人员建立网络，并会见潜在的雇主。在化学系化学合成计划的支持下，加州大学圣巴巴拉分校的特雷弗·海顿教授将对与生物无机化学、有机合成和纳米科学等不同主题相关的金属硫化物反应性进行广泛的调查。特别是，他的实验室将探索金属硫化物与一氧化氮的反应，以努力了解NO/H_2S“串扰”过程，这是生物系统中NO与硫化物/氢硫化物之间的一系列反应，被认为在细胞信号传递和免疫反应中发挥重要作用。此外，他们还将探索单硫过碳酸酯片段(即SOC(O)O-二阴离子)作为S原子转移试剂的能力。该物种被预测为一个热力学上比元素硫更强大的S原子源，但应该具有良好的动力学稳定性。最后，他们将合成并分离出一系列原子精确的不同大小的硫化镍纳米团簇(APNC)。这一系列的团簇旨在揭示过渡金属纳米团簇中的顺磁性是如何出现的。开放壳层APNC可以具有单分子磁体(SMM)行为，并已被提议用作新的自旋量子比特。这一奖项反映了NSF的法定使命，并通过使用基金会的智力优势和更广泛的影响审查标准进行评估，被认为值得支持。

With the support of the Chemical Synthesis program in the Division of Chemistry, Professor Trevor Hayton of the University of California-Santa Barbara will explore the chemistry of sulfide-containing metal complexes. Sulfur plays a key role in industry, medicine, and biology. Underpinning much of this chemistry is the reactivity of metal sulfides. In this project, Professor Hayton will develop several new applications of metal sulfides, including nitric oxide delivery, catalytic sulfur-atom transfer for organic synthesis, and quantum computing. This research will provide excellent training to undergraduate and graduate students in the synthesis and characterization of air-sensitive metal complexes, preparing them for careers in academia, industry, and the national laboratory system. In addition, Professor Hayton will develop a student-led virtual seminar series to introduce students to cutting-edge nanoscience. This series will allow undergraduate students, in particular, to network with researchers from other institutions and meet potential employers. With the support of the Chemical Synthesis program in the Division of Chemistry, Professor Trevor Hayton of the University of California Santa Barbara will perform a wide-ranging investigation into metal sulfide reactivity related to a diverse set of topics, including bioinorganic chemistry, organic synthesis, and nanoscience. In particular, his laboratory will explore the reactions metal sulfides with nitric oxide in an effort to understand the NO/H2S “crosstalk” process, a suite of reactions between NO and sulfide/hydrosulfide in biological systems that is thought to play an important role in cell signaling and the immune response. Additionally, they will explore the ability of the monothiopercarbonate fragment (i.e., the SOC(O)O-dianion) to function as a S-atom transfer reagent. This species is predicted to be a thermodynamically more powerful S-atom source than elemental sulfur, yet should feature good kinetic stability. Finally, they will synthesize and isolate a series of nickel sulfide atomically-precise nanoclusters (APNCs) of varying size. This series of clusters is designed to uncover how paramagnetism emerges in transition metal nanoclusters. Open shell APNCs can feature single molecule magnet (SMM) behavior and have been proposed to function as novel spin qubits.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.