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Synthesis of Isoreticular Zinc(II)‐Phosphonocarboxylate Frameworks and Their Application in the Friedel–Crafts Benzylation Reaction
Author(s) -
Deng Mingli,
Ling Yun,
Xia Bing,
Chen Zhenxia,
Zhou Yaming,
Liu Xiaofeng,
Yue Bin,
He Heyong
Publication year - 2011
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201101239
Subject(s) - sbus , chemistry , catalysis , selectivity , friedel–crafts reaction , zinc , medicinal chemistry , lewis acids and bases , ion , molecule , porosity , inorganic chemistry , nuclear chemistry , metal organic framework , organic chemistry , adsorption
Three isoreticular zinc(II)‐phosphonocarboxylate frameworks, namely {[Zn 3 (pbdc) 2 ] ⋅ 2 H 3 O} n (ZnPC‐2), {[Zn 3 (pbdc) 2 ] ⋅ Hpd ⋅ H 3 O ⋅ 4 H 2 O} n (Hpd@ZnPC‐2) and {[Co 1.5 Zn 1.5 (pbdc) 2 ] ⋅ 2 H 3 O} n (CoZnPC‐2) (H 4 pbdc=5‐phosphonobenzene‐1,3‐dicarboxylic acid, pd=pyrrolidine), were solvothermally synthesized. ZnPC‐2 has a 3D structure based on trinuclear Zn II clusters (Zn 3 ‐SBU) showing 3D interconnected channels. Hpd@ZnPC‐2 contains an isoreticular framework of ZnPC‐2 with small channels blocked by Hpd molecules. In CoZnPC‐2, Zn II ions in ZnPC‐2 are partially substituted by Co II ions. The Friedel–Crafts benzylation reactions were carried out over these isoreticular porous materials. The catalytic results reveal that ZnPC‐2 is an excellent heterogeneous Lewis acid catalyst with a high selectivity (>90 %) towards less bulky para ‐oriented products. The catalytic reaction has been proved to occur inside the pore of ZnPC‐2, and the immobilized Zn 3 ‐SBUs are the active sites.