@article { ISI:000296264700024, title = {Structural and gas adsorption study of a two-dimensional copper-tetrazole based metal-organic framework}, journal = {Current Science}, volume = {101}, number = {7}, year = {2011}, month = {OCT}, pages = {894-899}, publisher = {INDIAN ACAD SCIENCES}, address = {C V RAMAN AVENUE, SADASHIVANAGAR, P B \#8005, BANGALORE 560 080, INDIA}, abstract = {

A new two-dimensional (2D) metal organic framework, Cu-1(4-TBA)(1)(DMBP)(1).DMF (Cu-TBA-3), has been synthesized under solvothermal condition from transition metal cation Cu(II), predesigned ligand 4-(1H-tetrazole-5-yl)benzoic acid (4-TBA) and coligand 4,4{\textquoteright}-dimethy1-2,2{\textquoteright}-bipyridine (DMBP). The structure has been determined by single crystal X-ray crystallography which shows layered 2D structure with square shaped one-dimensional channels. Cu-TBA-3 shows 0.69 wt\% H-2 (at 77 K, 1 atm) and 1.65 mmol/g CO2 (at 298 K, 1 atm) uptake.

}, keywords = {CO2 capture, Hydrogen storage, metal-organic frameworks, microporous materials}, issn = {0011-3891}, author = {Pachfule, Pradip and Banerjee, Rahul} } @article { ISI:000308310100032, title = {Control of porosity by using isoreticular zeolitic imidazolate frameworks (IRZIFs) as a template for porous carbon synthesis}, journal = {Chemistry-A European Journal}, volume = {18}, number = {36}, year = {2012}, month = {SEP}, pages = {11399-11408}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

Herein, by using isoreticular zeolitic imidazolate frameworks (IRZIFs) as a template, we report the synthesis, morphology, and gas adsorption properties of porous carbon synthesized by a nanocasting method at 1000 degrees C, in which furfuryl alcohol (FA) was used as a carbon source. By using IRZIFs with variable porosity as templates, we could achieve control over the carbon porosity and H-2 and CO2 uptake. The resultant microporous carbon C-70, synthesized by using ZIF-70 as the template, is the most porous (Brunauer-Emmett-Teller (BET) surface area 1510 m(2)g(-1)). Carbon C-68, synthesized by using ZIF-68, has moderate porosity (BET surface area 1311 m(2)g(-1)), and C-69, synthesized by using ZIF-69, has the lowest porosity in this series (BET surface area 1171 m(2)g(-1)). The porous carbons C-70, C-68, and C-69, which have graphitic texture, have promising H2 uptake capacities of 2.37, 2.15, and 1.96 wt\%, respectively, at 77 K and 1 atm. Additionally, C-70, C-68, and C-69 show CO2 uptake capacities of 5.45, 4.98, and 4.54 mmolg(-1), respectively, at 273 K and 1 atm. The gas uptake trends shown by C-70, C-68, and C-69 clearly indicate the dependence of carbon porosity on the host template. Moreover, the as-synthesized carbons C-70, C-68, and C-69 show variable conductivity.

}, keywords = {Carbon, Hydrogen storage, metal-organic frameworks, microporous materials, zinc}, issn = {0947-6539}, doi = {10.1002/chem.201200957}, author = {Pachfule, Pradip and Biswal, Bishnu P. and Banerjee, Rahul} } @article { ISI:000298731200036, title = {Fluorinated metal-organic frameworks: advantageous for higher H-2 and CO2 adsorption or not?}, journal = {Chemistry-A European Journal}, volume = {18}, number = {2}, year = {2012}, month = {JAN}, pages = {688-694}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

The synthesis, structure, and gas adsorption properties of three new metalorganic frameworks (MOFs) designed from isonicotinic acid (INA) and its fluorinated analogue 3-fluoroisonicotinic acid (FINA) along with CoII as the metal center have been reported. Co-INA-1 ([Co3(INA)4(O)(C2H5OH)3][NO3].C2H5OH.3?H2O; INA=isonicotinic acid) and Co-INA-2 ([Co(INA)2].DMF) are structural isomers as are Co-FINA-1 ([Co3(FINA)4(O)(C2H5OH)2].H2O; FINA=3-fluoroisonicotinic acid) and Co-FINA-2 ([Co(FINA)2].H2O), but the most important thing to note here is that Co-INA-1 and Co-FINA-1 are isostructural as are Co-INA-2 and Co-FINA-2. The effect of partial introduction of fluorine atoms into the framework on the gas uptake properties of MOFs having similar structures has been analyzed experimentally and computationally in isostructural MOFs.

}, keywords = {cobalt, fluorine, Hydrogen storage, metal-organic frameworks, microporous materials, X-ray diffraction}, issn = {0947-6539}, doi = {10.1002/chem.201102295}, author = {Pachfule, Pradip and Chen, Yifei and Jiang, Jianwen and Banerjee, Rahul} } @article { ISI:000328437200053, title = {Hydrolytic conversion of a metal-organic polyhedron into a metal-organic framework}, journal = {Angewandte Chemie-International Edition}, volume = {52}, number = {51}, year = {2013}, month = {DEC}, pages = {13755-13759}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, keywords = {cage compounds, crystal engineering, hydrophobic effect, metal-organic frameworks, Self-assembly}, issn = {1433-7851}, doi = {10.1002/anie.201307486}, author = {Mallick, Arijit and Garai, Bikash and Diaz, David Diaz and Banerjee, Rahul} } @article { ISI:000325849000034, title = {Zeolitic imidazolate framework (ZIF)-derived, hollow-core, nitrogen-doped carbon nanostructures for oxygen-reduction reactions in PEFCs}, journal = {Chemistry-A European Journal}, volume = {19}, number = {28}, year = {2013}, month = {JUL}, pages = {9335-9342}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

The facile synthesis of a porous carbon material that is doped with iron-coordinated nitrogen active sites (FeNC-70) is demonstrated by following an inexpensive synthetic pathway with a zeolitic imidazolate framework (ZIF-70) as a template. To emphasize the possibility of tuning the porosity and surface area of the resulting carbon materials based on the structure of the parent ZIF, two other ZIFs, that is, ZIF-68 and ZIF-69, are also synthesized. The resulting active carbon material that is derived from ZIF-70, that is, FeNC-70, exhibits the highest BET surface area of 262m2g-1 compared to the active carbon materials that are derived from ZIF-68 and ZIF-69. The HR-TEM images of FeNC-70 show that the carbon particles have a bimodal structure that is composed of a spherical macroscopic pore (about 200nm) and a mesoporous shell. X-ray photoelectron spectroscopy (XPS) reveals the presence of Fe-N-C moieties, which are the primary active sites for the oxygen-reduction reaction (ORR). Quantitative estimation by using EDAX analysis reveals a nitrogen content of 14.5wt.\%, along with trace amounts of iron (0.1wt.\%), in the active FeNC-70 catalyst. This active porous carbon material, which is enriched with Fe-N-C moieties, reduces the oxygen molecule with an onset potential at 0.80V versus NHE through a pathway that involves 3.3-3.8e- under acidic conditions, which is much closer to the favored 4e- pathway for the ORR. The onset potential of FeNC-70 is significantly higher than those of its counterparts (FeNC-68 and FeNC-69) and of other reported systems. The FeNC-based systems also exhibit much-higher tolerance towards MeOH oxidation and electrochemical stability during an accelerated durability test (ADT). Electrochemical analysis and structural characterizations predict that the active sites for the ORR are most likely to be the insitu generated NFeN2+2/C moieties, which are distributed along the carbon framework.

}, keywords = {Doping, Electrochemistry, metal-organic frameworks, Nanostructures, oxygen-reduction reaction}, issn = {0947-6539}, doi = {10.1002/chem.201300145}, author = {Palaniselvam, Thangavelu and Biswal, Bishnu P. and Banerjee, Rahul and Kurungot, Sreekumar} } @article { ISI:000341831600037, title = {Evolution of an adenine-copper cluster to a highly porous cuboidal framework: solution-phase ripening and gas-adsorption properties}, journal = {Chemistry-A European Journal}, volume = {20}, number = {38}, year = {2014}, month = {SEP}, pages = {12262-12268}, publisher = {WILEY-V C H VERLAG GMBH}, type = {Article}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

The synthesis and directed evolution of a tetranu-clear copper cluster, supported by 8-mercapto-N9-propyladenine ligand, to a highly porous three-dimensional cubic framework in the solid state is reported. The structure of this porous framework was unambiguously characterized by Xray crystallography. The framework contains about 62\% solvent-accessible void; the presence of a free exocyclic amino group in the porous framework facilitates reversible adsorption of gas and solvent molecules. Oriented growth of framework in solution was also tracked by force and scanning electron microscopy studies, leading to identification of an intriguing ripening process, over a period of 30 days, which also revealed formation of cuboidal aggregates in solution. The elemental composition of these cuboidal aggregates was ascertained by EDAX analysis.

}, keywords = {cuboidal frameworks, gas adsorption, metal-organic frameworks, Ostwald ripening, solution-phase ripening}, issn = {0947-6539}, doi = {10.1002/chem.201403115}, author = {Venkatesh, V. and Pachfule, Pradip and Banerjee, Rahul and Verma, Sandeep} } @article { ISI:000340469800044, title = {Mechanical downsizing of a gadolinium(iii)-based metal-organic framework for anticancer drug delivery}, journal = {Chemistry-A European Journal}, volume = {20}, number = {33}, year = {2014}, month = {AUG}, pages = {10514-10518}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

A Gd-III-based porous metal-organic framework (MOF), Gd-pDBI, has been synthesized using fluorescent linker pDBI (pDBI=(1,4-bis(5-carboxy-1H-benzimidazole-2-yl)benzene)), resulting in a three-dimensional interpenetrated structure with a one-dimensional open channel (1.9x1.2nm) filled with hydrogen-bonded water assemblies. Gd-pDBI exhibits high thermal stability, porosity, excellent water stability, along with organic-solvent and mild acid and base stability with retention of crystallinity. Gd-pDBI was transformed to the nanoscale regime (ca. 140nm) by mechanical grinding to yield MG-Gd-pDBI with excellent water dispersibility (\>90min), maintaining its porosity and crystallinity. In vitro and in vivo studies on MG-Gd-pDBI revealed its low blood toxicity and highest drug loading (12wt\%) of anticancer drug doxorubicin in MOFs reported to date with pH-responsive cancer-cell-specific drug release.

}, keywords = {ball-milling, doxorubicin, drug delivery, metal-organic frameworks, nanocarriers}, issn = {0947-6539}, doi = {10.1002/chem.201402244}, author = {Kundu, Tanay and Mitra, Shouvik and Patra, Prasun and Goswami, Arunava and Diaz, David Diaz and Banerjee, Rahul} } @article { ISI:000349384300005, title = {Single crystal-to-single crystal site-selective postsynthetic metal exchange in a Zn-MOF based on semi-rigid tricarboxylic acid and access to bimetallic MOFs}, journal = {Chemistry-A European Journal}, volume = {21}, number = {7}, year = {2015}, month = {FEB}, pages = {2759-2765}, publisher = {WILEY-V C H VERLAG GMBH}, address = {BOSCHSTRASSE 12, D-69469 WEINHEIM, GERMANY}, abstract = {

The metal ions in a neutral Zn-MOF constructed from tritopic triacid H3L with inherent concave features, rigid core, and peripheral flexibility are found to exist in two distinct SBUs, that is, 0D and 1D. This has allowed site-selective postsynthetic metal exchange (PSME) to be investigated and reactivities of the metal ions in two different environments in coordination polymers to be contrasted for the first time. Site-selective transmetalation of Zn ions in the discrete environment is shown to occur in a single crystal-to-single crystal (SCSC) fashion, with metal ions such as Fe3+, Ru3+, Cu2+, Co2+, etc., whereas those that are part of 1D SBU sustain structural integrity, leading to novel bimetallic MOFs, which are inaccessible by conventional approaches. To the best of our knowledge, site-selective postsynthetic exchange of an intraframework metal ion in a MOF that contains metal ions in discrete as well as polymeric SBUs is heretofore unprecedented.

}, keywords = {coordination polymers, metal-exchange, metal-organic frameworks, Metathesis, X-ray crystallography}, issn = {0947-6539}, doi = {10.1002/chem.201406098}, author = {Bajpai, Alankriti and Chandrasekhar, Pujari and Govardhan, Savitha and Banerjee, Rahul and Moorthy, Jarugu Narasimha} }