Journal
DALTON TRANSACTIONS
Volume 46, Issue 40, Pages 14002-14011Publisher
ROYAL SOC CHEMISTRY
DOI: 10.1039/c7dt02809a
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Funding
- Advanced Graduate Program on Molecular Systems for Devices, Program for Leading Graduate Schools
- German Federal Ministry of Education and Research (BMBF Project) [05K16D1]
- DFG [FOR2433]
- JSPS KAKENHI [JP16H06519]
- Grants-in-Aid for Scientific Research [15H03787, 16H06519] Funding Source: KAKEN
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Controlled nucleation in a micromixer and further crystal growth were used to synthesize Ni-2(2,6-ndc)(2)dabco (2,6-ndc - 2,6-naphthalenedicarboxylate, dabco - 1,4-diazabicyclo[2.2.2] octane), also termed DUT-8(Ni) (DUT = Dresden University of Technology), with narrow particle size distribution in a range of a few nm to several mu m. The crystal size was found to significantly affect the switching characteristics, in particular the gate opening pressure in nitrogen adsorption isotherms at 77 K for this highly porous and flexible network. Below a critical size of about 500 nm, a type la isotherm typical of rigid MOFs is observed, while above approximately 1000 nm a pronounced gating behaviour is detected, starting at p/p(0) = 0.2. With increasing crystal size this transition gate becomes steeper indicating a more uniform distribution of activation energies within the crystal ensemble. At an intermediate size (500-1000 nm), the DUT-8(Ni) crystals close during activation but cannot be reopened by nitrogen at 77 K possibly indicating monodomain switching.
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