Direct observation of molecular-level template action leading to self-assembly of a porous framework.
The molecular steps involved in the self-assembly of Cu(3)(BTC)(2) (BTC=1,3,5-benzenetricarboxylic acid) metal-organic frameworks that enclose Keggin-type H(3)PW(12)O(40) heteropolyacid molecules were unraveled by using solution (17)O, (31)P, and (183)W NMR spectroscopy, small-angle X-ray scattering, near-IR spectroscopy, and dynamic light scattering. In aqueous solution, complexation of Cu(2+) ions with Keggin-type heteropolyacids was observed. Cu(2+) ions are arranged around the Keggin structure so that linking through benzenetricarboxylate groups results in the formation of the Cu(3)(BTC)(2) MOF structure HKUST-1. This is a unique instance in which a templating mechanism that relies on specific molecular-level matching and leads to explicit nanoscale building units can be observed in situ during formation of the synthetic nanoporous material.
Centre for Surface Science and Catalysis, Department of Microbial and Molecular Systems, K. U. Leuven, Kasteelpark Arenberg 23, Leuven B-3001, Belgium. Sneha.BajpeRohita@biw.kuleuven.be
Sneha R
SR
Bajpe
Christine E A
CE
Kirschhock
Alexander
A
Aerts
Eric
E
Breynaert
Gregory
G
Absillis
Tatjana N
TN
Parac-Vogt
Lars
L
Giebeler
Johan A
JA
Martens
D003300:Copper / Q000737:chemistry*; D007477:Ions / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008670:Metals / Q000737:chemistry*; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D016062:Porosity; D012996:Solutions; D013056:Spectrophotometry, Ultraviolet; D017973:Tungsten Compounds / Q000737:chemistry*; D000099294:Polyoxometalates
D003300:Copper; D007477:Ions; D008670:Metals; D009942:Organometallic Compounds; D012996:Solutions; D017973:Tungsten Compounds; C102296:polyoxometalate I; D000099294:Polyoxometalates