TY  - JOUR
A1  - Debatin, Franziska
A1  - Behrens, Karsten
A1  - Weber, Jens
A1  - Baburin, Igor A.
A1  - Thomas, Arne
A1  - Schmidt, Johannes
A1  - Senkovska, Irena
A1  - Kaskel, Stefan
A1  - Kelling, Alexandra
A1  - Hedin, Niklas
A1  - Bacsik, Zoltan
A1  - Leoni, Stefano
A1  - Seifert, Gotthard
A1  - Jäger, Christian
A1  - Günter, Christina
A1  - Schilde, Uwe
A1  - Friedrich, Alwin
A1  - Holdt, Hans-Jürgen
T1  - An isoreticular family of microporous metal-organic frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate Syntheses, structures and properties
JF  - Chemistry - a European journal
N2  - We report on a new series of isoreticular frameworks based on zinc and 2-substituted imidazolate-4-amide-5-imidate (IFP-14, IFP=imidazolate framework Potsdam) that form one-dimensional, microporous hexagonal channels. Varying R in the 2-substitued linker (R=Me (IFP-1), Cl (IFP-2), Br (IFP-3), Et (IFP-4)) allowed the channel diameter (4.01.7 angstrom), the polarisability and functionality of the channel walls to be tuned. Frameworks IFP-2, IFP-3 and IFP-4 are isostructural to previously reported IFP-1. The structures of IFP-2 and IFP-3 were solved by X-ray crystallographic analyses. The structure of IFP-4 was determined by a combination of PXRD and structure modelling and was confirmed by IR spectroscopy and 1H MAS and 13C CP-MAS NMR spectroscopy. All IFPs showed high thermal stability (345400?degrees C); IFP-1 and IFP-4 were stable in boiling water for 7 d. A detailed porosity analysis was performed on the basis of adsorption measurements by using various gases. The potential of the materials to undergo specific interactions with CO2 was investigated by measuring the isosteric heats of adsorption. The capacity to adsorb CH4 (at 298 K), CO2 (at 298 K) and H2 (at 77 K) at high pressure were also investigated. In situ IR spectroscopy showed that CO2 is physisorbed on IFP-14 under dry conditions and that both CO2 and H2O are physisorbed on IFP-1 under moist conditions.
KW  - adsorption
KW  - metal- organic frameworks
KW  - microporous materials
KW  - N
KW  - O ligands
KW  - zinc
Y1  - 2012
U6  - https://doi.org/10.1002/chem.201200889
SN  - 0947-6539
VL  - 18
IS  - 37
SP  - 11630
EP  - 11640
PB  - Wiley-VCH
CY  - Weinheim
ER  - 
TY  - JOUR
A1  - Behrens, Karsten
A1  - Mondal, Suvendu Selchar
A1  - Nöske, Robert
A1  - Baburin, Igor A.
A1  - Leoni, Stefano
A1  - Günter, Christina
A1  - Weber, Jens
A1  - Holdt, Hans-Jürgen
T1  - Microwave-Assisted Synthesis of Defects Metal-Imidazolate-Amide-Imidate Frameworks and Improved CO2 Capture
JF  - Inorganic chemistry
N2  - In this work, we report three isostructural 3D frameworks, named IFP-11 (R = Cl), IFP-12 (R = Br), and IFP-13 (R = Et) (IFP = Imidazolate Framework Potsdam) based on a cobalt(II) center and the chelating linker 2-substituted imidazolate-4-amide-5-imidate. These chelating ligands were generated in situ by partial hydrolysis of 2-substituted 4,5-dicyanoimidazoles under microwave (MW)-assisted conditions in DMF. Structure determination of these IFPs was investigated by IR spectroscopy and a combination of powder X-ray diffraction (PXRD) with structure modeling. The structural models were initially built up from the single-crystal X-ray structure determination of IFP-5 (a cobalt center and 2-methylimidazolate-4-amide-5-imidate linker based framework) and were optimized by using density functional theory calculations. Substitution on position 2 of the linker (R = Cl, Br, and Et) in the isostructural IFP-11, -12, and -13 allowed variation of the potential pore window in 1D hexagonal channels (3.8 to 1.7 angstrom A). The potential of the materials to undergo specific interactions with CO2 was measured by the isosteric heat adsorption. Further, we resynthesized zinc based IFPs, namely IFP-1 = Me), IFP-2 (R = Cl), IFP-3 (R = Br), and IFP-4 (R = Et), and cobalt based IFP-5 under MW-assisted conditions with higher yield. The transition from a nucleation phase to the pure crystalline material of IFP-1 in MW-assisted synthesis depends on reaction time. IFP-1, -3, and -5, which are synthesized by MW-assisted conditions, showed an enhancement of N-2 and CO2, compared to the analogous conventional electrical (CE) heating method based materials due to crystal defects.
Y1  - 2015
U6  - https://doi.org/10.1021/acs.inorgchem.5b01952
SN  - 0020-1669
SN  - 1520-510X
VL  - 54
IS  - 20
SP  - 10073
EP  - 10080
PB  - American Chemical Society
CY  - Washington
ER  -