Covalent Organic Frameworks as Porous Pigments for Photocatalytic Metal-Free C–H Borylation

Covalent organic frameworks (COFs) are highly promising as heterogeneous photocatalysts due to their tunable structures and optoelectronic properties. Though COFs have been used as heterogeneous photocatalysts, they have mainly been employed in water splitting, carbon dioxide reduction, and hydrogen evolution reactions. A few examples in organic synthesis using metal-anchored COF photocatalysts were reported. Herein, we report highly stable β-keto-enamine-based COFs as photocatalysts for metal-free C–B bond formation reactions. Three different COFs have been availed for this purpose. Their photocatalysis performances have been monitored for 12 different substrates, like quinolines, pyridines, and pyrimidines. All the COFs showcase moderate-to-high yields (up to 96%) depending upon the substrate’s molecular functionality. High crystallinity, a large surface area, a low band gap, and a suitable band position result in the highest catalytic activity of TpAzo COF. The thorough mechanistic investigation further highlights the crucial role of light-harvesting capacity, charge separation efficiency, and current density during catalysis. The light absorbance capacity of the COF plays a critical role during catalysis as yields are maximized near the COF’s absorption maxima. The high photostability of the as-synthesized COFs offers their reusability for several (>5) catalytic cycles

Porosity Prediction through Hydrogen Bonding in Covalent Organic Frameworks

Easy and bulk-scale syntheses of two-dimensional (2D) covalent organic frameworks (COFs) represent an enduring challenge in material science. Concomitantly, the most critical aspect is to precisely control the porosity and crystallinity of these robust structures. Disparate complementary approaches such as solvothermal synthesis have emerged recently and are fueled in part by the usage of different modulators and acids that have enriched the COF library. Yet, the fundamental understanding of the integral processes of 2D COF assembly, including their growth from nucleating sites and the origin of periodicity, is an intriguing chemical question that needs to be answered. To address these cardinal questions, a green and easy-to-perform approach of COF formation has been delineated involving acid-diamine salt precursors. The role of hydrogen bonding [<i>d</i>_av(N_amine–H···O_acid); <i>d</i>_av signifies the average N_amine–H···O_acid distances, i.e., the average distance from the H atom of the amine to the O atom of the acid] present in the acid-diamine salts in improving the COFs’ crystallinity and porosity has further been decoded by thorough crystallographic analyses of the salt molecules. What is particularly noteworthy is that we have established the hydrogen-bonding distances <i>d</i>_av(N_amine–H···O_acid) in the acid-diamine salts that are pivotal in maintaining the reversibility of the reaction, which mainly facilitates highly crystalline and porous COF formation. Moreover, this reactant-structure to the product-quality relationship has further been utilized for the synthesis of highly crystalline and porous COFs that are unattainable by other synthetic means

Porosity Prediction through Hydrogen Bonding in Covalent Organic Frameworks

Easy and bulk-scale syntheses of two-dimensional (2D) covalent organic frameworks (COFs) represent an enduring challenge in material science. Concomitantly, the most critical aspect is to precisely control the porosity and crystallinity of these robust structures. Disparate complementary approaches such as solvothermal synthesis have emerged recently and are fueled in part by the usage of different modulators and acids that have enriched the COF library. Yet, the fundamental understanding of the integral processes of 2D COF assembly, including their growth from nucleating sites and the origin of periodicity, is an intriguing chemical question that needs to be answered. To address these cardinal questions, a green and easy-to-perform approach of COF formation has been delineated involving acid-diamine salt precursors. The role of hydrogen bonding [<i>d</i>_av(N_amine–H···O_acid); <i>d</i>_av signifies the average N_amine–H···O_acid distances, i.e., the average distance from the H atom of the amine to the O atom of the acid] present in the acid-diamine salts in improving the COFs’ crystallinity and porosity has further been decoded by thorough crystallographic analyses of the salt molecules. What is particularly noteworthy is that we have established the hydrogen-bonding distances <i>d</i>_av(N_amine–H···O_acid) in the acid-diamine salts that are pivotal in maintaining the reversibility of the reaction, which mainly facilitates highly crystalline and porous COF formation. Moreover, this reactant-structure to the product-quality relationship has further been utilized for the synthesis of highly crystalline and porous COFs that are unattainable by other synthetic means

Porosity Prediction through Hydrogen Bonding in Covalent Organic Frameworks

Easy and bulk-scale syntheses of two-dimensional (2D) covalent organic frameworks (COFs) represent an enduring challenge in material science. Concomitantly, the most critical aspect is to precisely control the porosity and crystallinity of these robust structures. Disparate complementary approaches such as solvothermal synthesis have emerged recently and are fueled in part by the usage of different modulators and acids that have enriched the COF library. Yet, the fundamental understanding of the integral processes of 2D COF assembly, including their growth from nucleating sites and the origin of periodicity, is an intriguing chemical question that needs to be answered. To address these cardinal questions, a green and easy-to-perform approach of COF formation has been delineated involving acid-diamine salt precursors. The role of hydrogen bonding [<i>d</i>_av(N_amine–H···O_acid); <i>d</i>_av signifies the average N_amine–H···O_acid distances, i.e., the average distance from the H atom of the amine to the O atom of the acid] present in the acid-diamine salts in improving the COFs’ crystallinity and porosity has further been decoded by thorough crystallographic analyses of the salt molecules. What is particularly noteworthy is that we have established the hydrogen-bonding distances <i>d</i>_av(N_amine–H···O_acid) in the acid-diamine salts that are pivotal in maintaining the reversibility of the reaction, which mainly facilitates highly crystalline and porous COF formation. Moreover, this reactant-structure to the product-quality relationship has further been utilized for the synthesis of highly crystalline and porous COFs that are unattainable by other synthetic means

Porosity Prediction through Hydrogen Bonding in Covalent Organic Frameworks

Easy and bulk-scale syntheses of two-dimensional (2D) covalent organic frameworks (COFs) represent an enduring challenge in material science. Concomitantly, the most critical aspect is to precisely control the porosity and crystallinity of these robust structures. Disparate complementary approaches such as solvothermal synthesis have emerged recently and are fueled in part by the usage of different modulators and acids that have enriched the COF library. Yet, the fundamental understanding of the integral processes of 2D COF assembly, including their growth from nucleating sites and the origin of periodicity, is an intriguing chemical question that needs to be answered. To address these cardinal questions, a green and easy-to-perform approach of COF formation has been delineated involving acid-diamine salt precursors. The role of hydrogen bonding [<i>d</i>_av(N_amine–H···O_acid); <i>d</i>_av signifies the average N_amine–H···O_acid distances, i.e., the average distance from the H atom of the amine to the O atom of the acid] present in the acid-diamine salts in improving the COFs’ crystallinity and porosity has further been decoded by thorough crystallographic analyses of the salt molecules. What is particularly noteworthy is that we have established the hydrogen-bonding distances <i>d</i>_av(N_amine–H···O_acid) in the acid-diamine salts that are pivotal in maintaining the reversibility of the reaction, which mainly facilitates highly crystalline and porous COF formation. Moreover, this reactant-structure to the product-quality relationship has further been utilized for the synthesis of highly crystalline and porous COFs that are unattainable by other synthetic means

Access to Silicon(II)– and Germanium(II)–Indium Compounds

Despite the remarkable ability of N-heterocyclic silylene to act as a Lewis base and form stable Lewis adducts with group 13 elements such as boron, aluminum, and gallium, there has been no such comparable investigation with indium and the realization of a stable silylene–indium complex has still remained elusive. Similarly, a germylene–indium complex is also presently unknown. We describe herein the reactions of [PhC­(N<i>t</i>Bu)₂SiN­(SiMe₃)₂] (<b>1</b>) and [PhC­(N<i>t</i>Bu)₂GeN­(SiMe₃)₂] (<b>4</b>) with InCl₃ and InBr₃ that have resulted in the first silylene–indium complexes, [PhC­(N<i>t</i>Bu)₂Si­{N­(SiMe₃)₂}→InCl₃] (<b>2</b>) and [PhC­(N<i>t</i>Bu)₂Si­{N­(SiMe₃)₂}→InBr₃] (<b>3</b>), as well as the first germylene–indium complexes, [PhC­(N<i>t</i>Bu)₂Ge­{N­(SiMe₃)₂}→InCl₃] (<b>5</b>) and [PhC­(N<i>t</i>Bu)₂Ge­{N­(SiMe₃)₂}→InBr₃] (<b>6</b>). The solid-state structures of all species have been validated by single-crystal X-ray diffraction studies. Note that <b>5</b> and <b>6</b> are the first structurally characterized organometallic compounds that feature a Ge–In single bond (apart from the compounds in Zintl phases). Theoretical calculations reveal that the Si­(II)→In bonds in <b>2</b> and <b>3</b> and the Ge­(II)→In bonds in <b>5</b> and <b>6</b> are dative bonds

Multistimuli-Responsive Interconvertible Low-Molecular Weight Metallohydrogels and the in Situ Entrapment of CdS Quantum Dots Therein

Two low molecular weight metallohydrogels (ZALA and CALA) have been synthesized from an amino-acid-based ligand precursor (LA) and two different metal salts [zinc acetate dihydrate (ZA) and cadmium acetate dihydrate (CA), respectively. These two hydrogels show a unique chemically stimulated interconversion to each other via a reversible gel–sol–gel pathway. This programmable gel–sol reversible system satisfies logic operations of a basic Boolean logic (INHIBIT) gate. Also, these hydrogels can be degraded into different MOF phases at room temperature spontaneously or in the presence of chloride and bromide salts (NaCl and NaBr.). CdS quantum dots can be grown inside the CALA gel matrix (CdS@CALA) in the presence of small amount of Na₂S. This CdS doped gel exhibits time dependent tunable emission (white to yellow to orange) as a consequence of a slow agglomeration process of the entrapped quantum dots inside the gel matrix. This luminescence property also reflects the corresponding gel derived MOFs (obtained either by self-degradation of CdS@CALA or via anion induction) as well. This, to the best of our knowledge, is probably the simplest way to make a CdS quantum dot based composite material where CdS is entrapped within the gel and the gel-derived MOF matrix

A Covalent Organic Framework for Cooperative Water Oxidation

The future of water-derived hydrogen as the “sustainable energy source” straightaway bets on the success of the sluggish oxygen-generating half-reaction. The endeavor to emulate the natural photosystem II for efficient water oxidation has been extended across the spectrum of organic and inorganic combinations. However, the achievement has so far been restricted to homogeneous catalysts rather than their pristine heterogeneous forms. The poor structural understanding and control over the mechanistic pathway often impede the overall development. Herein, we have synthesized a highly crystalline covalent organic framework (COF) for chemical and photochemical water oxidation. The interpenetrated structure assures the catalyst stability, as the catalyst’s performance remains unaltered after several cycles. This COF exhibits the highest ever accomplished catalytic activity for such an organometallic crystalline solid-state material where the rate of oxygen evolution is as high as ∼26,000 μmol L–1 s–1 (second-order rate constant k ≈ 1650 μmol L s–1 g–2). The catalyst also proves its exceptional activity (k ≈ 1600 μmol L s–1 g–2) during light-driven water oxidation under very dilute conditions. The cooperative interaction between metal centers in the crystalline network offers 20–30-fold superior activity during chemical as well as photocatalytic water oxidation as compared to its amorphous polymeric counterpart

Constructing Ultraporous Covalent Organic Frameworks in Seconds via an Organic Terracotta Process

Research on covalent organic frameworks (COFs) has recently gathered significant momentum by the virtue of their predictive design, controllable porosity, and long-range ordering. However, the lack of solvent-free and easy-to-perform synthesis processes appears to be the bottleneck toward their greener fabrication, thereby limiting their possible potential applications. To alleviate such shortcomings, we demonstrate a simple route toward the rapid synthesis of highly crystalline and ultraporous COFs in seconds using a novel salt-mediated crystallization approach. A high degree of synthetic control in interlayer stacking and layer planarity renders an ordered network with a surface area as high as 3000 m² g^–1. Further, this approach has been extrapolated for the continuous synthesis of COFs by means of a twin screw extruder and <i>in situ</i> processes of COFs into different shapes mimicking the ancient terracotta process. Finally, the regular COF beads are shown to outperform the leading zeolites in water sorption performance, with notably facile regeneration ability and structural integrity