Direct Observation of Modulated Radical Spin States in Metal–Organic Frameworks by Controlled Flexibility

化学 激进的 二聚体 金属有机骨架 光化学 桥联配体 电子顺磁共振 结晶学 晶体结构 物理化学 有机化学 核磁共振 物理 吸附
作者
Xiaofeng Chen,Haomiao Xie,Emmaline R. Lorenzo,Charles J. Zeman,Yue Qi,Zoha H. Syed,Aaron E. B. S. Stone,Yao Wang,Subhadip Goswami,Peng Li,Timur İslamoğlu,Emily A. Weiss,Joseph T. Hupp,George C. Schatz,Michael R. Wasielewski,Omar K. Farha
出处
期刊:Journal of the American Chemical Society [American Chemical Society]
卷期号:144 (6): 2685-2693 被引量:38
标识
DOI:10.1021/jacs.1c11417
摘要

Owing to their switchable spin states and dynamic electronic character, organic-based radical species have been invoked in phenomena unique to a variety of fields. When incorporated in solid state materials, generation of organic radicals proves challenging due to aggregation. Metal-organic frameworks (MOFs) are promising candidates for immobilization and stabilization of organic radicals because of the tunable spatial arrangement of organic linkers and metal nodes, which sequesters the reactive species. Herein, a flexible, redox-active tetracarboxylic acid linker bearing two imidazole units was chosen to construct a new Zr6-MOF, NU-910, with scu topology. By exploiting the structural flexibility of NU-910, we successfully modulate the dynamics between an isolated organic radical species and an organic radical π-dimer species in the MOF system. Single-crystal X-ray diffraction analysis reveals that through solvent exchange from N,N-diethylformamide to acetone, NU-910 undergoes a structural contraction with interlinker distances decreasing from 8.32 Å to 3.20 Å at 100 K. Organic radical species on the bridging linkers are generated via UV light irradiation. Direct observation of temperature-induced spin switches from an isolated radical species to a magnetically silent radical π-dimer in NU-910 after irradiation in the solid state was achieved via variable-temperature single-crystal X-ray diffraction and variable-temperature electron paramagnetic resonance spectroscopy. Ultraviolet-visible-near infrared spectroscopy and density functional theory calculations further substantiated the formation of a radical cation π-dimer upon irradiation. This work demonstrates the potential of using flexible MOFs as a platform to modulate radical spin states in the solid phase.
最长约 10秒,即可获得该文献文件

科研通智能强力驱动
Strongly Powered by AbleSci AI
更新
PDF的下载单位、IP信息已删除 (2025-6-4)

科研通是完全免费的文献互助平台,具备全网最快的应助速度,最高的求助完成率。 对每一个文献求助,科研通都将尽心尽力,给求助人一个满意的交代。
实时播报
1秒前
2秒前
Anyixx完成签到 ,获得积分10
3秒前
清爽尔安发布了新的文献求助10
5秒前
6秒前
丫丫发布了新的文献求助10
7秒前
huangyikun发布了新的文献求助10
7秒前
叔铭完成签到,获得积分10
8秒前
大个应助ZONG采纳,获得10
10秒前
10秒前
Ma完成签到,获得积分10
11秒前
孙燕应助猪猪hero采纳,获得10
11秒前
会发光的小灰灰完成签到,获得积分10
11秒前
板凳儿cc发布了新的文献求助10
11秒前
黑色天使发布了新的文献求助10
12秒前
12秒前
激情的代曼完成签到,获得积分10
12秒前
13秒前
16秒前
缓慢手机完成签到,获得积分10
16秒前
丫丫完成签到,获得积分10
16秒前
17秒前
时尚俊驰发布了新的文献求助10
17秒前
耍酷的冷雪完成签到,获得积分10
18秒前
wanci应助baonali采纳,获得10
20秒前
ZONG发布了新的文献求助10
21秒前
wuy发布了新的文献求助10
21秒前
123完成签到,获得积分10
22秒前
23秒前
saisyo发布了新的文献求助10
24秒前
隐形曼青应助炸胡娃娃采纳,获得30
25秒前
坦率白萱应助wwl采纳,获得10
25秒前
NexusExplorer应助小晓采纳,获得10
25秒前
26秒前
26秒前
123发布了新的文献求助10
27秒前
搞怪的紫易完成签到,获得积分10
27秒前
WYQ完成签到,获得积分10
27秒前
幸福大白发布了新的文献求助10
29秒前
玩命的凝天完成签到,获得积分10
29秒前
高分求助中
A new approach to the extrapolation of accelerated life test data 1000
ACSM’s Guidelines for Exercise Testing and Prescription, 12th edition 500
‘Unruly’ Children: Historical Fieldnotes and Learning Morality in a Taiwan Village (New Departures in Anthropology) 400
Indomethacinのヒトにおける経皮吸収 400
Phylogenetic study of the order Polydesmida (Myriapoda: Diplopoda) 370
基于可调谐半导体激光吸收光谱技术泄漏气体检测系统的研究 350
Robot-supported joining of reinforcement textiles with one-sided sewing heads 320
热门求助领域 (近24小时)
化学 材料科学 医学 生物 工程类 有机化学 生物化学 物理 内科学 纳米技术 计算机科学 化学工程 复合材料 遗传学 基因 物理化学 催化作用 冶金 细胞生物学 免疫学
热门帖子
关注 科研通微信公众号,转发送积分 3989444
求助须知:如何正确求助?哪些是违规求助? 3531531
关于积分的说明 11254250
捐赠科研通 3270191
什么是DOI,文献DOI怎么找? 1804901
邀请新用户注册赠送积分活动 882105
科研通“疑难数据库(出版商)”最低求助积分说明 809174