Solvent induced single-crystal to single-crystal structural transformation and concomitant transmetalation in a 3D cationic Zn(<scp>ii</scp>)-framework

Sen, Susan; Neogi, Subhadip; Rissanen, Kari; Bharadwaj, Parimal K.

doi:10.1039/c4cc09955a

Cited by 54 publications

(26 citation statements)

References 36 publications

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“…The bond lengths and bond angles of selected bonds have been provided in Table . It is worth mentioning that the Zn(1)⋅⋅⋅Zn(2) distances in 1 (3.215 Å) and 2 (3.259 Å) are nearly equal and are significantly longer than those found in tetracarboxylates Zn 2 [(O 2 CR)] 4 (3.008 Å), but shorter than those observed in dicarboxylates: Zn 2 [(O 2 CR)] 2 (3.782) . The lattice packing behaviour of both the compounds are very similar and hence the self‐assembly behaviour of only 2 is presented in here in Figure c.…”

Section: Resultsmentioning

confidence: 78%

Zinc Dialkylhydroxybenzoates with Unusual Structures: First Example of a Discrete Three‐Blade Paddle‐Wheel and a Solvent Engulfed Coordination Polymer

2016

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Sterically encumbered 4‐hydroxy‐3,5‐diisopropylbenzoic acid (H2diphba), bearing a carboxylic acid, a phenol and two iso‐propyl substituents, has been investigated for the first time as a ligand and supramolecular synthon to isolate eight Zn(II) complexes, [Zn2(Hdiphba)3(OAc)(L)] (L=DMF(1) or pyz (2)), [Zn(Hdiphba)2(2,2′‐bpy)] (3), [Zn(Hdiphba)2(1,10‐phen)] (4), [Zn(Hdiphba)2(pz)2] (5) and [Zn2(Hdiphba)2(μ2‐dmpz)2(Hdmpz)2] (6), [Zn(Hdiphba)2(4,4′‐bpy)]n⋅4nCH3OH (7.4nCH3OH), [Zn2(Hdiphba)4(4,4′‐azobpy)(H2O)2] (8⋅H2diphba), which have been structurally characterized. Compounds 1 and 2 are rare examples of symmetrically bridged triple‐blade molecular tricarboxylate paddle‐wheels which self‐assemble into hexameric units. Compounds 3, 4 and 5 are mononuclear complexes, bearing two exposed phenolic –OH groups self‐assembled into 2‐D arrays via both hydrogen bonding and π‐π stacking interactions. Compound 6 is a rare example of bis‐pyrazolate bridged dinuclear Zn(II) complex with two pyrazole N−H and two phenolic ‐OH groups on the molecular periphery to form hydrogen bonds. The use of 4,4’‐bpy leading to a zig‐zag 1‐D polymer 7 composed of [Zn(Hdiphba)2(4,4’‐bpy)]n chains, positioned 10.77 Å apart. The 1‐D channels of 7 are occupied by hydrogen bonded methanol with a rare (CH3OH)4 cluster as the repeating unit. Compound 8 is a discrete bimetallic complex, isolated with a free H2diphba ligand. The photoluminescence spectra of 1–8 exhibit ligand centered emission at around 325 nm.

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Section: Resultsmentioning

confidence: 78%

Zinc Dialkylhydroxybenzoates with Unusual Structures: First Example of a Discrete Three‐Blade Paddle‐Wheel and a Solvent Engulfed Coordination Polymer

2016

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“…The presence of secondaryb uilding units (SBUs) and supramolecular buildingb locks (SBBs), based on metal clusters, is ah elpful approacht om aintaining framework integrity after am etal-exchange reaction. [5] By using this technique, multifunctional MOFs can be obtainedt hat may or may not be accessibleb yt he de novo method. Moreover,t ransmetalation can be used to fabricate the interior and exterioro fM OFs with improved properties.…”

Section: Introductionmentioning

confidence: 99%

Significant Gas Adsorption and Catalytic Performance by a Robust Cu^II–MOF Derived through Single‐Crystal to Single‐Crystal Transmetalation of a Thermally Less‐Stable Zn^II–MOF

Pal

Neogi

et al. 2015

Chemistry A European J

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By using a bent tetracarboxylic acid ligand that incorporates a pendent-NH2 functional group, a 3D Zn(II)-framework (1) based on Zn2 (CO2)4 secondary building units and Zn12 (CO2)24 supramolecular building blocks has been synthesized. Framework 1 is thermally less stable, which precludes its application as a porous framework for gas adsorption or catalytic studies. This framework undergoes single-crystal to single-crystal transmetalation to give isostructural 1Cu. Unlike 1, the Cu(II) analogue is very stable and can be activated by removing metal-bound lattice solvent molecules by heating to afford 1Cu'. The activated 1Cu' exhibits excellent H2 storage (2.29 wt%) at 77 K and a high 32.1 wt% CO2 uptake at 273 K. Additionally, it displays significant selectivity for CO2 adsorption over N2 and H2 and can catalyse size-selective Knoevenagel condensation reactions.

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“…[9,10] Another kind of indirect synthetic method called solvent-mediated structural transformation involves the dissolution of the initial frameworks and subsequent formation of new frameworks under the help of newly introduced molecules and/or ions. [11][12][13][14][15][16][17][18] Among few reports about solvent-mediated structural transformation with simultaneous transmetalation, incomplete transmetalation [19] is rarer than complete transmetalation. [20][21][22][23][24][25] efficient desulfurization adsorbent as the homometallic Cu-HKUST-1 in removing thiophene (0.142 mmol S per gram of adsorbent).…”

Section: Introductionmentioning

confidence: 99%

Metal‐ion‐dependent, Solvent‐mediated Structural Transformation and Simultaneous Partial Transmetalation of an srs Framework into Desulfurization‐efficient Co‐Cu‐HKUST‐1

Zhang

Tan

et al. 2020

Zeitschrift anorg allge chemie

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Co 2 (BTC)(Cl)(DMA) 3 ] (1) (BTC 3-= benzene-1,3,5-tricarboxylate, DMA = N,N-dimethylacetamide) obtained from the reaction between Co 2+ and H 3 BTC in DMA features a three-dimensional srs framework built of 3-connected {Co 2 (COO) 3 } as secondary building units and BTC 3as spacers. When exposed to DMA solution of Cu(NO 3) 2 , 1 was progressively transformed into the first heterometallic Co-Cu-HKUST-1 ([Co 0.14 Cu 2.86 (BTC) 2 ]) (2) of such kind via unusually solvent-mediated structural transformation and simultaneous partial transmetalation. While the mechanism for such conversion is proposed based on systematic studies, 2 was revealed to be an equally

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Solvent induced single-crystal to single-crystal structural transformation and concomitant transmetalation in a 3D cationic Zn(ii)-framework

Cited by 54 publications

References 36 publications

Zinc Dialkylhydroxybenzoates with Unusual Structures: First Example of a Discrete Three‐Blade Paddle‐Wheel and a Solvent Engulfed Coordination Polymer

Zinc Dialkylhydroxybenzoates with Unusual Structures: First Example of a Discrete Three‐Blade Paddle‐Wheel and a Solvent Engulfed Coordination Polymer

Significant Gas Adsorption and Catalytic Performance by a Robust Cu^II–MOF Derived through Single‐Crystal to Single‐Crystal Transmetalation of a Thermally Less‐Stable Zn^II–MOF

Metal‐ion‐dependent, Solvent‐mediated Structural Transformation and Simultaneous Partial Transmetalation of an srs Framework into Desulfurization‐efficient Co‐Cu‐HKUST‐1

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Solvent induced single-crystal to single-crystal structural transformation and concomitant transmetalation in a 3D cationic Zn(ii)-framework

Cited by 54 publications

References 36 publications

Zinc Dialkylhydroxybenzoates with Unusual Structures: First Example of a Discrete Three‐Blade Paddle‐Wheel and a Solvent Engulfed Coordination Polymer

Zinc Dialkylhydroxybenzoates with Unusual Structures: First Example of a Discrete Three‐Blade Paddle‐Wheel and a Solvent Engulfed Coordination Polymer

Significant Gas Adsorption and Catalytic Performance by a Robust CuII–MOF Derived through Single‐Crystal to Single‐Crystal Transmetalation of a Thermally Less‐Stable ZnII–MOF

Metal‐ion‐dependent, Solvent‐mediated Structural Transformation and Simultaneous Partial Transmetalation of an srs Framework into Desulfurization‐efficient Co‐Cu‐HKUST‐1

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Significant Gas Adsorption and Catalytic Performance by a Robust Cu^II–MOF Derived through Single‐Crystal to Single‐Crystal Transmetalation of a Thermally Less‐Stable Zn^II–MOF