Tailoring rhodium-based metal-organic layers for parahydrogen-induced polarization:achieving 20%polarization of^(1)H in liquid phase  

作　　者：Jiawei Chen Qi Zhang Tao Chen Zeyu Zheng Yuhang Song Huichong Liu Ziqiao Chen Jing Wang Haoshang Wang Huijun Sun Xinchang Wang Zhong Chen Cheng Wang Zhongqun Tian 

机构地区：[1]State Key Laboratory of Physical Chemistry of Solid Surfaces,School of Electronic Science and Engineering,Department of Chemistry,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China [2]College of Biology and Environmental Engineering,Zhejiang Shuren University,Hangzhou 310015,China [3]Innovation Laboratory for Sciences and Technologies of Energy Materials of Fujian Province(IKKEM),Xiamen 361005,China

出　　处：《National Science Review》2025年第1期247-258,共12页国家科学评论(英文版)

基　　金：supported by the National Natural Science Foun-dation of China(22125502,22071207,22121001,21971217 and 22272133);the Fundamental Research Funds for the Central Universities(20720220011,20720240053 and 20720240070).

摘　　要：Heterogeneous catalysts for parahydrogen-induced polarization(HET-PHIP)would be useful for producing highly sensitive contrasting agents for magnetic resonance imaging(MRI)in the liquid phase,as they can be removed by simple filtration.Although homogeneous hydrogenation catalysts are highly efficient for PHIP,their sensitivity decreases when anchored on porous supports due to slow substrate diffusion to the active sites and rapid depolarization within the channels.To address this challenge,we explored 2D metal-organic layers(MOLs)as supports for active Rh complexes with diverse phosphine ligands and tunable hydrogenation activities,taking advantage of the accessible active sites and chemical adaptability of the MOLs.By adjusting the electronic properties of phosphines,TPP-MOL-Rh-dppb(TPP=tris(4-carboxy lpheny l)phosphine),featuring aκ2-connected di(phosphine)ligand,generated hyperpolarized styrene achieving an over-2400-fold signal enhancement and a polarization level of 20%for^(1)H in methanol-d_(4)solution.The TPP-MOL-Rh-dppb effectively inherited the high efficiency and pairwise addition of its homogenous catalyst while maintaining the heterogeneity of MOLs.This work demonstrates the potential of 2D phosphine-functionalized MOLs as heterogeneous solid support for HET-PHIP.

关 键 词：metal-organic layers heterogeneous catalysts parahydrogen-induced polarization HYPERPOLARIZATION nuclear magnetic resonance 

分 类 号：O63[理学—高分子化学]