Porphyrin Grafting on a Mercapto-Equipped Zr(IV)-Carboxylate Framework Enhances Photocatalytic Hydrogen Production

Diao, Yingxue1,2; Xu, Nanfeng3,4; Li, Mu-Qing1,5; Zhu, Xunjin3,4; Xu, Zhengtao1

2020-09-08

10.1021/acs.inorgchem.0c01744

INORGANIC CHEMISTRY   影响因子和分区

0020-1669

1520-510X

We employ facile aromatic nucleophilic substitution between the mercapto (-SH) and arylfluoro (Ar-F) groups to achieve extensive and robust cross-linking of a coordination host by porphyrin guests that also serve the purpose of versatile postsynthetic functionalization. For this, a tritopic linker with three trident-like thiol-flanked carboxyl units are reacted with ZrOCl2 center dot 8H(2)O to afford a two-dimensional (3,6-connected) net. The wide aperture of the porous framework solid, together with its stability in both air and boiling water, facilitates the entry of bulky metalloporphyrin guests and the subsequent property studies. On the porphyrin side, four pentafluorophenyl (C6F5-) groups offer multiple fluoro groups to facilitate their replacement by the thiol groups from the host net. The inserted metalloporphyrin bridges impart to the metal-organic framework (MOF) host stable and recyclable activities for photocatalytic hydrogen production. We also disclose an improvement in synthetic methodology, in which BBr3 is used to simultaneously cleave they ester and benzyl thioether groups to more efficiently access thiol-equipped carboxylic acid building block.

SCI ; EI

英语

NI期刊

其他

GRF grant of the Research Grants Council of Hong Kong SAR[11303519] ; Hong Kong Baptist University[FRG2-17-18-068] ; Interinstitutional Collaborative Research Scheme[RC-ICRS-18-19-01A] ; Interdisciplinary Research Matching Scheme[RC-IRMS/16/17/02CHEM]

Chemistry

Chemistry, Inorganic & Nuclear

WOS:000570979900083

AMER CHEMICAL SOC

20203709167085

Zirconium compounds ; Carboxylation ; Hydrogen production ; Bromine compounds ; Metal-Organic Frameworks ; Photocatalytic activity

Gas Fuels:522 ; Metallurgy:531.1 ; Physical Chemistry:801.4 ; Chemical Reactions:802.2 ; Organic Compounds:804.1

CHEMISTRY

Web of Science

1.City Univ Hong Kong, Dept Chem, Kowloon, Hong Kong, Peoples R China
2.City Univ Hong Kong, Dept Mat Sci & Engn, Kowloon, Hong Kong, Peoples R China
3.Hong Kong Baptist Univ, Dept Chem, Kowloon Tong, Hong Kong, Peoples R China
4.Hong Kong Baptist Univ, Inst Adv Mat, Kowloon Tong, Hong Kong, Peoples R China
5.Southern Univ Sci & Technol, Dept Mat Sci & Engn, Shenzhen 518055, Guangdong, Peoples R China

Diao, Yingxue,Xu, Nanfeng,Li, Mu-Qing,et al. Porphyrin Grafting on a Mercapto-Equipped Zr(IV)-Carboxylate Framework Enhances Photocatalytic Hydrogen Production[J]. INORGANIC CHEMISTRY,2020,59(17):12643-12649.

Diao, Yingxue,Xu, Nanfeng,Li, Mu-Qing,Zhu, Xunjin,&Xu, Zhengtao.(2020).Porphyrin Grafting on a Mercapto-Equipped Zr(IV)-Carboxylate Framework Enhances Photocatalytic Hydrogen Production.INORGANIC CHEMISTRY,59(17),12643-12649.

Diao, Yingxue,et al."Porphyrin Grafting on a Mercapto-Equipped Zr(IV)-Carboxylate Framework Enhances Photocatalytic Hydrogen Production".INORGANIC CHEMISTRY 59.17(2020):12643-12649.