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Multi Variant Surface Mounted Metal–Organic Frameworks
Author(s) -
Liu Bo,
Tu Min,
Zacher Denise,
Fischer Roland A.
Publication year - 2013
Publication title -
advanced functional materials
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 6.069
H-Index - 322
eISSN - 1616-3028
pISSN - 1616-301X
DOI - 10.1002/adfm.201202996
Subject(s) - dabco , materials science , crystallite , metal organic framework , octane , crystallography , adsorption , monolayer , chemical engineering , nanotechnology , chemistry , organic chemistry , engineering , metallurgy
Hybrid surface mounted metal–organic frameworks (h‐SURMOFs) of multi variant core‐shell (cs) and core–shell–shell (css) structures (SURMOF A ‐ B and A ‐ B ‐ C , A : [Cu 2 (bdc) 2 (dabco)]; B : [Cu 2 (NH 2 ‐bdc) 2 (dabco)]; C : [Cu 2 (ndc) 2 (dabco)], bdc = 1,4‐benzenedicarboxylate; NH 2 ‐bdc = 2‐amino‐1,4‐benzenedicarboxylate; ndc = 1,4‐naphtalenedicarboxylate; dabco = 1,4‐diazabicyclo[2.2.2]octane) with specific crystallographic [001] orientation and incorporated amino groups at a controllable depth within the bulk are deposited via liquid phase epitaxial (LPE) approach on pyridyl‐terminated self‐assembled monolayers (SAM). The location of the (amino) functionality can be precisely controlled through tuning the thickness (number of deposition cycles) of each sub‐multilayer block according to the LPE deposition protocol. The chemo‐selective and location‐specific post deposition (chemical) modification of the amino groups in the cs and css‐type h‐SURMOF samples is achieved. The h‐SURMOFs allow one to probe functional groups at certain location in the volume of hybrid MOF crystallites attached to surfaces as thin film coatings. Multiplex adsorption kinetics of FPI (FPI = 4‐fluorophenyl isothiocyanate) is observed in h‐SURMOFs due to their multi‐variant pore structures in samples of A‐B and A‐B‐C . Conceptually, the stepwise LPE growth method enables fabrication of hybrid SURMOFs and incorporation of multi‐variant functionalities into one homogeneous thin film material, providing precisely tunable pore environment for selective adsorption, separation, etc.