Reactions of (<i>E</i>)‑5-(Pyridin-4-yl-methyleneamino)isophthalic Acid (LH₂) with Triorganotin Oxides and −Chloride. Formation of One-Dimensional- and Two-Dimensional-Coordination Polymers

The reaction of (n-Bu3Sn)2O with (E)-5-(pyridin-4-yl-methyleneamino)­isophthalic acid (LH2) in a stoichiometric ratio of 1:1 resulted in the formation of a 2D coordination polymer [(n-Bu3Sn)2(μ-L)]n (1). The structure of 1 contains a 36-membered macrocycle as its repeating building block. The reactions of Me3SnCl or (Ph3Sn)2O with LH2, on the other hand, result in the generation of [(Me3Sn)2(μ-L)­(H2O)]n (a neutral 1D coordination polymer) (2) and [(Ph3Sn)­(μ-L)­(Et3NH)]n (an anionic 1D coordination polymer) (3), respectively. Compounds 1–3 show a rich supramolecular architecture in their solid state as a result of multiple secondary interactions

Reactions of (<i>E</i>)‑5-(Pyridin-4-yl-methyleneamino)isophthalic Acid (LH₂) with Triorganotin Oxides and −Chloride. Formation of One-Dimensional- and Two-Dimensional-Coordination Polymers

The reaction of (<i>n</i>-Bu₃Sn)₂O with (<i>E</i>)-5-(pyridin-4-yl-methyleneamino)­isophthalic acid (LH₂) in a stoichiometric ratio of 1:1 resulted in the formation of a 2D coordination polymer [(<i>n</i>-Bu₃Sn)₂(μ-L)]_<i>n</i> (<b>1</b>). The structure of <b>1</b> contains a 36-membered macrocycle as its repeating building block. The reactions of Me₃SnCl or (Ph₃Sn)₂O with LH₂, on the other hand, result in the generation of [(Me₃Sn)₂(μ-L)­(H₂O)]_<i>n</i> (a neutral 1D coordination polymer) (<b>2</b>) and [(Ph₃Sn)­(μ-L)­(Et₃NH)]_<i>n</i> (an anionic 1D coordination polymer) (<b>3</b>), respectively. Compounds <b>1</b>–<b>3</b> show a rich supramolecular architecture in their solid state as a result of multiple secondary interactions

Stabilizing the [RSn(μ₂‑O)SnR] Motif through Intramolecular N→Sn Coordination. Synthesis and Characterization of [(RSn)₂(μ₂‑O)(μ₂‑FcCOO)₂(η-FcCOO)₂]·THF and {(RSn)₂(μ₂‑O)[(<i>t-</i>BuO)₂PO₂]₂Cl₂}·THF·2H₂O (R = 2‑(Phenylazo)phenyl)

The reactions of RSnCl₃ (<b>1</b>; R = 2-(phenylazo)­phenyl) with FcCOOH or di-<i>tert</i>-butyl phosphate in refluxing THF afforded the monoorganodistannoxanes [(RSn)₂(μ₂-O)­(μ₂-FcCOO)₂(η-FcCOO)₂]·THF (<b>2</b>) and {(RSn)₂(μ₂-O)­[(<i>t-</i>BuO)₂PO₂]₂Cl₂}·THF·2H₂O (<b>3</b>). The molecular structure of <b>2</b> contains seven-coordinate tin centers in a distorted-pentagonal-bipyramidal geometry, while <b>3</b> contains six-coordinate tin centers in a distorted-octahedral geometry. In the dinuclear compounds <b>2</b> and <b>3</b> the two tin centers are bridged by a μ₂-O unit, affording a rare Sn–O–Sn motif among monoorganostannoxanes. In addition, each tin is also intramolecularly coordinated to the nitrogen atom of the 2-phenylazophenyl substituent (N→Sn). Further, in <b>2</b>, the two tin centers are bridged by two isobidentate ferrocenecarboxylate ligands; each tin center also is bound to a chelating ferrocenecarboxylate ligand. On the other hand, in <b>3</b>, while the two tin centers are bridged by two isobidentate di-<i>tert</i>-butyl phosphate ligands, each tin center also has a terminal chloride ligand

Stabilizing the [RSn(μ₂‑O)SnR] Motif through Intramolecular N→Sn Coordination. Synthesis and Characterization of [(RSn)₂(μ₂‑O)(μ₂‑FcCOO)₂(η-FcCOO)₂]·THF and {(RSn)₂(μ₂‑O)[(<i>t-</i>BuO)₂PO₂]₂Cl₂}·THF·2H₂O (R = 2‑(Phenylazo)phenyl)

The reactions of RSnCl₃ (<b>1</b>; R = 2-(phenylazo)­phenyl) with FcCOOH or di-<i>tert</i>-butyl phosphate in refluxing THF afforded the monoorganodistannoxanes [(RSn)₂(μ₂-O)­(μ₂-FcCOO)₂(η-FcCOO)₂]·THF (<b>2</b>) and {(RSn)₂(μ₂-O)­[(<i>t-</i>BuO)₂PO₂]₂Cl₂}·THF·2H₂O (<b>3</b>). The molecular structure of <b>2</b> contains seven-coordinate tin centers in a distorted-pentagonal-bipyramidal geometry, while <b>3</b> contains six-coordinate tin centers in a distorted-octahedral geometry. In the dinuclear compounds <b>2</b> and <b>3</b> the two tin centers are bridged by a μ₂-O unit, affording a rare Sn–O–Sn motif among monoorganostannoxanes. In addition, each tin is also intramolecularly coordinated to the nitrogen atom of the 2-phenylazophenyl substituent (N→Sn). Further, in <b>2</b>, the two tin centers are bridged by two isobidentate ferrocenecarboxylate ligands; each tin center also is bound to a chelating ferrocenecarboxylate ligand. On the other hand, in <b>3</b>, while the two tin centers are bridged by two isobidentate di-<i>tert</i>-butyl phosphate ligands, each tin center also has a terminal chloride ligand

Bismuth Phosphinates: Temperature-dependent Formation of a Macrocycle and a 1D Coordination Polymer

<div><p></p><p>The reaction of Ph₃Bi with a sterically hindered phosphinic acid, 1,1,2,3,3- pentamethyltrimethylene phosphinic acid, {<i>cyc</i>P(O)OH·2H₂O} at two different temperatures, one at refluxing conditions and another at room temperature in THF have been investigated. At refluxing conditions, cleavage of two Bi-C bonds (of BiPh₃) leads to the formation of a 16-membered macrocycle [(PhBi)₄(<i>cyc</i>PO₂)₈] (<b>1</b>). On the other hand, the reaction at room temperature leads to only cleavage of one Bi-C bond affording a 1D polymer [(Ph₂Bi)(<i>cyc</i>PO₂)]_n, (1,1,2,3,3-pentamethyltrimethylene phosphinate is denoted as <i>cyc</i>PO₂) (<b>2</b>). Both the complexes were characterized by single crystal X-ray diffraction. In both of these complexes the phosphinate ligands are present in anisobidentate (bridging) coordination mode. </p></div

Redox Switching Behavior in Resistive Memory Device Designed Using a Solution-Processable Phenalenyl-Based Co(II) Complex: Experimental and DFT Studies

We herein report a novel square-planar complex [CoIIL], which was synthesized using the electronically interesting phenalenyl-derived ligand LH2 = 9,9′-(ethane-1,2-diylbis­(azanediyl))­bis­(1H-phenalen-1-one). The molecular structure of the complex is confirmed with the help of the single-crystal X-ray diffraction technique. [CoIIL] is a mononuclear complex where the Co­(II) ion is present in the square-planar geometry coordinated by the chelating bis-phenalenone ligand. The solid-state packing of [CoIIL] complex in a crystal structure has been explained with the help of supramolecular studies, which revealed that the π···π stacking present in the [CoIIL] complex is analogous to the one present in tetrathiafulvalene/tetracyanoquinodimethane charge transfer salt, well-known materials for their unique charge carrier interfaces. The [CoIIL] complex was employed as the active material to fabricate a resistive switching memory device, indium tin oxide/CoIIL/Al, and characterized using the write-read-erase-read cycle. The device has interestingly shown a stable and reproducible switching between two different resistance states for more than 2000 s. Observed bistable resistive states of the device have been explained by corroborating the electrochemical characterizations and density functional theory studies, where the role of the CoII metal center and π-conjugated phenalenyl backbone in the redox-resistive switching mechanism is proposed

Designing a Redox Noninnocent Phenalenyl-Based Copper(II) Complex: An Autotandem Catalyst for the Selective Oxidation of Polycyclic Aromatic Hydrocarbons (PAHs)

A square-planar [CuIIL] complex 1, based on the redox-active phenalenyl unit LH2 = 9,9′-(ethane-1,2-diylbis­(azanediyl))­bis­(1H-phenalen-1-one), is prepared and structurally characterized by single-crystal X-ray diffraction analysis. Complex 1 crystallizes at room temperature with the P1 space group. The molecular structure of 1 reveals the presence of intriguing C–H···Cu intermolecular anagostic interactions of the order ∼2.7715 Å. Utilizing the presence of anagostic interactions and the free nonbonding molecular orbitals (NBMOs) of the closed-shell phenalenyl unit in 1, the oxidation reactions of some industrially important polycyclic aromatic hydrocarbons (PAHs) in the presence of the [CuIIL] complex under very mild conditions have been reported. The direct conversion of anthracene-9-carbaldehyde to 9,10-anthraquinone in one step concludes that the catalyst shows dual activity in the chemical transformations. This also includes the first report of a “single-step” catalytic transformation of pyrene-1-carbaldehyde to the synthetically difficult pyren-4-ol, a precursor for the synthesis of several novel fluorescent probes for cell imaging

Molecular Memory Switching Device Based on a Tetranuclear Organotin Sulfide Cage [(RSn^IV)₄(μ-S)₆]·2CHCl₃·4H₂O (R = 2‑(Phenylazo)phenyl): Synthesis, Structure, DFT Studies, and Memristive Behavior

RSnCl3 (R = 2-phenylazophenyl) on reaction with Na2S·9H2O in a 1:1 mixture of acetone and methanol afforded a tetranuclear monoorganotin sulfide cage [(RSnIV)4(μ-S)6]·2CHCl3·4H2O (R = 2-phenylazophenyl) (1). Complex 1 crystallizes in the monoclinic space group P2/n. The molecular structure of 1 contains five-coordinate tin centers in distorted trigonal bipyramidal geometry. Complex 1 is monoorganotin sulfide derivative having a tetranuclear double-decker cage-like structure. In 1, four tin centers are bridged by a μ2-S unit affording a ubiquitous Sn–S–Sn motif among monoorganotin sulfide compounds. In addition, each tin also has intramolecular coordination to a nitrogen atom of a 2-phenylazophenyl substituent (N → Sn). The DFT calculation suggests that the complex 1 involves mainly ligand based transitions. The complex 1 based device was studied for its electrical behavior and was found to show stable, reproducible memristive behavior with an on–off ratio of 103, which suggests that the complex 1 is a promising material for memory device applications

Recyclable Polymer Supported DMAP Catalyzed Cascade Synthesis of α‑Pyrones

Polymer-supported catalysts have emerged as one of the sustainable and cost-effective alternatives in organic synthetic chemistry. We have developed the first polymer-supported DMAP catalyzed one-pot synthesis of diversely substituted α-pyrones. The cascade approach involves C5 conjugate addition of 5H-oxazol-4-ones to α,β-unsaturated-β-ketoesters followed by lactonization/elimination

Recyclable Polymer Supported DMAP Catalyzed Cascade Synthesis of α‑Pyrones

Polymer-supported catalysts have emerged as one of the sustainable and cost-effective alternatives in organic synthetic chemistry. We have developed the first polymer-supported DMAP catalyzed one-pot synthesis of diversely substituted α-pyrones. The cascade approach involves C5 conjugate addition of 5H-oxazol-4-ones to α,β-unsaturated-β-ketoesters followed by lactonization/elimination