Determination of the Preassembled Nucleating Units That Are Critical for the Crystal Growth of the Metal-Organic Framework CdIF-4.
Identifying the form and role of the chemical species that traverse the stages of crystallization is critical to understanding the formation process of coordination polymers. Herein, we report the combined use of in situ atomic force microscopy and mass spectrometry to identify preformed, complex, cadmium 2-ethylimidazole containing solution species in the growth solution of the cadmium 2-ethylimidazolate metal-organic framework CdIF-4, and show that they are critical in the surface nucleation for the crystal growth of this material. Surface nucleation appears to be instigated by these [Cdx (CH3 CO2 )y (C5 H7 N2 /C5 H8 N2 )z ]-containing solution species and not by sole addition of the ligand molecules. The CH3 CO2 (-) or Cd(CH3 CO2 )2 groups of the former are substituted subsequently as the framework growth proceeds. Our greater understanding of such solution species and their role in crystallization will guide future syntheses of designed functional coordination polymers.
School of Chemistry, The University of Manchester, Brunswick Street, Manchester, M13 9PL, UK.
Raghidah
R
Wagia
School of Chemistry, The University of Manchester, Brunswick Street, Manchester, M13 9PL, UK.
Ilya
0000-0001-6502-5530
I
Strashnov
School of Chemistry, The University of Manchester, Brunswick Street, Manchester, M13 9PL, UK.
Michael W
0000-0002-1443-8818
MW
Anderson
School of Chemistry, The University of Manchester, Brunswick Street, Manchester, M13 9PL, UK. m.attfield@manchester.ac.uk.
Martin P
0000-0001-6508-1751
MP
Attfield
atomic force microscopy; coordination polymers; crystal growth; metal-organic frameworks; nucleation