Dopant-controlled crystallization in metal-organic frameworks: The role of copper(II) in zinc 1,4-benzenedicarboxylate

Cantwell G. Carson, Jason Ward, Xiao Tao Liu, Justin Schwartz, Rosario A. Gerhardt, Rina Tannenbaum

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12 Scopus citations


A series of Zn-Cu 1,4-benzenedicarboxylate(bdc) metal organic frameworks(MOF) have been synthesized by introducing N,N-dimethylformamide(DMF) solutions of 1,4-benzenedicarboxylic acid to metal salt solutions with a range of concentrations of Cu(NO 3) 2 and Zn(NO 3) 2 across the entire composition range. At the Zn-rich side of the range, the presence of Cu(II) had the effect of changing the polymorph of the solid from the predominantly P2 1/n structure, associated with MOF-2, to the C2/m structure, shared with Cu(bdc). There was an associated change in crystal morphology that accompanied the addition of a Cu salt impurity. BET surface area measurements of the thermally desolvated product showed that the surface area of the Zn(bdc) increased with the addition of Cu. At the Cu-rich side, magnetic susceptibility measurements indicated that the presence of the Zn impurity increased the fraction of paramagnetic Cu centers, suggesting the formation of a large fraction of heterometallic secondary building units(hSBU) in the framework.

Original languageEnglish (US)
Pages (from-to)15322-15328
Number of pages7
JournalJournal of Physical Chemistry C
Issue number29
StatePublished - Jul 26 2012

All Science Journal Classification (ASJC) codes

  • Electronic, Optical and Magnetic Materials
  • Energy(all)
  • Physical and Theoretical Chemistry
  • Surfaces, Coatings and Films


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