Hydride Transfer-Based CO2 Reduction Catalysis: Navigating Metal Hydride to Organic Hydride in the Catalytic Loop.

ConspectusThe reductive conversion of carbon dioxide (CO2) into value-added products is a process of immense importance. In the context of rising CO2 concentration in the atmosphere and the detrimental effects it is having on the biosphere, use of alternative fuels which can offer a low-carbon or carbon-neutral pathway for storage and utilization of low-carbon energy by maintaining the net atmospheric CO2 concentration might be a prospective solution. Among the wide variety of reduced products that can be obtained from CO2, formic acid and formate salts are particularly important due to their ability to be used as an alternative fuel or a reversible hydrogen storage material. Utilization of molecular catalysts for CO2 conversion offers several advantages such as high selectivity, mechanistic clarity, versatility, and stability, making them attractive for thermochemical and electro/photochemical CO2 reduction processes. The presence of N-heterocyclic carbene (NHC) ligands in transition-metal-based molecular catalysts enhances the stability of the catalysts under harsh reaction conditions, such as high pressure, high temperature, and reductive environments, providing crucial benefits for sustained catalytic activity and longevity. Though the development of metal complex-based catalysts is essential to addressing the challenge of CO2 reduction, the possibility of using purely organic compounds as catalysts for this transformation is lucrative from the aspect of developing a truly sustainable protocol with photosynthesis being its biggest inspiration. We begin this Account by examining our systematic development of molecular metal complexes based on NHC ligands for the chemical upgradation of CO2 to formic acid/formate salt. In such cases, the ability of NHCs to act as strong σ-donor ligands for a greater hydride transfer propensity is discussed and analyzed. The reports range from catalytic ambient- and high-pressure CO2 hydrogenation to CO2 transfer-hydrogenation. Coupling of CO2 capture methodologies with CO2 conversion is also discussed. A case is made for the heterogenization of one of the highly efficient metal-NHC catalysts to develop a self-supported single-site catalyst for practical applications. Finally, our recent success of developing a novel organic catalyst system inspired from the natural NADP+/NADPH-based hydride-transfer redox couple that is active in photosynthetic CO2 reduction has been discussed. This catalyst is designed based on a bis-imidazolium-embedded heterohelicene with a central pyridine ring and is capable of electrocatalytically converting CO2 to HCO2H with TON values 100-1000 times greater than the existing reported values achieved so far by organic catalysts. Overall, we believe that the results of hydride transfer-based CO2 reduction catalysis presented in this Account hold significant implications beyond our work and have the potential for motivating future research toward further development in this important field.

Unveiling N-Fused Nitreniums as Potent Catalytic Photooxidants.

The first example of a hitherto-unknown facet of catalytic photooxidant capability of nitrenium cations is reported herein. The fundamental limitation of inability of the traditional and reported nitreniums to achieve the excited-state redox potential beyond +2.0 V (vs Ag/AgCl), the primary requirement for a powerful photooxidant, is addressed in this work by developing a structurally unique class of N-fused nitrenium cations, with the required structural engineering involving extensive π-conjugation through ring fusion at the nitrenium site, which enabled significant lowering of the LUMO energy and easy reduction at the excited state (excited-state redox potential up to +2.5 V vs Ag/AgCl), facilitated by effective delocalization/stabilization of the generated radical. This finding opens a new way to discover novel and useful (photo)catalytic properties of nitrenium cations beyond just Lewis acidity.

Three-Way Control on Product Selectivity in Electrocatalytic CO2 Reduction Reaction Using a Single Molecular Co-NHC Catalyst.

For a long time, molecular electrocatalysts have been developed to reduce CO2 efficiently to value-added products such as CO and HCO2H, along with H2; however, selectivity remained as a major issue. Recent work toward addressing this issue showed that several different catalysts could be used to achieve product selectivity. It is desirable that instead of using different catalysts for specific products, a single catalyst should be able to produce the target products by subtle tuning of the reaction conditions. Toward this objective, herein we presented the organometallic Co electrocatalyst Co-NHCU and successfully utilized it in the electrochemical CO2 reduction reaction (CO2RR) to produce CO, H2, and HCO2H with notable selectivity. The reduction of CO2 selectively produced CO with 81 ± 2% Faradaic efficiency (FE) in the presence of 5% H2O as a proton source. The selectivity was changed toward H2 with 80 ± 3% FE when 1.5 M triethylamine was added as an additive in the presence of 10% H2O as a proton source. In the presence of 1.0 M morpholine as an external additive, the CO2-saturated solution containing 10% trifluoroethanol as a proton source generates 55 ± 5% HCO2H as the predominant product, with H2 as a competitive side product. It was found that the combined effect of the proton source and the additive in association with the nature of the Co-NHCU catalyst changed the selectivity of the products in this reaction.

Orchestrated Octuple C-H Activation: A Bottom-Up Topology Engineering Approach toward Stimuli-Responsive Double-Heptagon-Embedded Wavy Polycyclic Heteroaromatics.

Curiosity-driven innovations on the design and synthesis of nonplanar polycyclic aromatic/heteroaromatic compounds with new molecular topologies unfold exciting opportunities for harnessing their intriguing supramolecular properties and thereby the development of novel functional organic materials. This work presents such an innovative synthetic concept of a bottom-up molecular topology engineering through a unique orchestrated octuple C-H activation reaction, toward the rapid synthesis of a novel class of double heptagon-incorporated nitrogen-doped laterally-fused polycyclic compounds with rarely reported wavy structural configuration. The profound impact of the molecular wavy structures of these compounds on their properties is manifested by weak and tunable solid-state intermolecular interactions controlling the electronic properties of the materials, leading to reversibly switchable fluorochromism in the solid state and thin films with mechanical force and solvent vapors as external stimuli, thereby indicating their potential applicability in rewritable fluorescent optical recording media, security papers, mechanosensors, volatile organic compound (VOC) sensors etc.

Exploiting the NADP+/NADPH-like Hydride-Transfer Redox Cycle with Bis-Imidazolium-Embedded Heterohelicene for Electrocatalytic Hydrogen Evolution Reaction.

Generation of clean energy in a viable manner demands efficient and sustainable catalysts. One prospective method of clean energy generation is the electrochemical hydrogen evolution reaction (HER). Over the years, various transition metal-based complexes/polymeric organic materials were utilized in HER. However, the use of a redox-active small organic molecule as a catalyst for HER has not been explored well. The requirements of a strongly acidic solution, very high overpotential, and stability under acidic conditions pose several challenges for applying organic electrocatalysts for HER. Considering these challenges, herein, we demonstrated an NADP+-like organic system (NADP+ = nicotinamide adenine dinucleotide phosphate), a bis-imidazolium-fused heterohelicene, which acts as a catalyst for HER with mild acid (acetic acid) as a proton source at moderate overpotential. The unique structural backbone of this dicationic heterohelicene allowed to exploit the NADP+/NADPH-type (NADPH = reduced nicotinamide adenine dinucleotide phosphate) hydride transfer-based redox cycle efficiently under the applied conditions, where the NADPH-like hydride intermediate transfers the hydride to the proton of the mild acid to generate H2. The Faradaic efficiency and turnover number for the present HER were achieved up to 85 ± 5% and 50 ± 3, respectively. In addition, the maximum turnover frequency, TOFmax, value of 410 s-1 was observed, which is around 400 times that obtained for the existing reported NADP+-like organic compounds used as catalysts for HER. Thorough mechanistic studies were conducted experimentally and computationally to establish a plausible catalytic cycle. This advancement could help in designing efficient organic electrocatalysts for HER from a mild proton source.

Bis-Imidazolium-Embedded Heterohelicene: A Regenerable NADP+ Cofactor Analogue for Electrocatalytic CO2 Reduction.

Biomimetic NAD(P)H-type organic hydride donors have recently been advocated as potential candidates to act as metal-free catalysts for fuel-forming reactions such as the reduction of CO2 to formic acid and methanol, similar to the natural photosynthesis process of fixing CO2 into carbohydrates. Although these artificial synthetic organic hydrides are extensively used in organic reduction chemistry in a stoichiometric manner, translating them into catalysts has been challenging due to problems associated with the regeneration of these hydride species under applied reaction conditions. A recent discovery of the possibility of their regeneration under electrochemical conditions via a proton-coupled electron-transfer pathway triggered intense research to accomplish their catalytic use in electrochemical CO2 reduction reactions (eCO2RR). However, success is yet to be realized to term them as "true" catalysts, as the typical turnover numbers (TONs) of the eCO2RR processes on inert electrodes for the production of formic acid and/or methanol reported so far are still in the order of 10-3-10-2; thus, sub-stoichiometric only! Herein, we report a novel class of structurally engineered heterohelicene-based organic hydride donor with a proof-of-principle demonstration of catalytic electrochemical CO2 reduction reaction showing a significantly improved activity with more than stoichiometric turnover featuring a 100-1000-fold enhancement of the existing TON values. Mechanistic investigations suggested the critical role of the two cationic imidazolium motifs along with the extensive π-conjugation present in the backbone of the heterohelicene molecules in accessing and stabilizing various radical species involved in the generation and transfer of hydride, via multielectron-transfer steps in the electrochemical process.

Directly Knitted Hierarchical Porous Organometallic Polymer-Based Self-Supported Single-Site Catalyst for CO2 Hydrogenation in Water.

In recent times, heterogenization of homogeneous molecular catalysts onto various porous solid support structures has attracted significant research focus as a method for combining the advantages of both homogeneous as well as heterogeneous catalysis. The design of highly efficient, structurally robust and reusable heterogenized single-site catalysts for the CO2 hydrogenation reaction is a critical challenge that needs to be accomplished to implement a sustainable and practical CO2 -looped renewable energy cycle. This study demonstrated a heterogenized catalyst [Ir-HCP-(B/TPM)] containing a molecular Ir-abnormal N-heterocyclic carbene (Ir-aNHC) catalyst self-supported by hierarchical porous hyper-crosslinked polymer (HCP), in catalytic hydrogenation of CO2 to inorganic formate (HCO2 - ) salt that is a prospective candidate for direct formate fuel cells (DFFC). By employing this unique and first approach of utilizing a directly knitted HCP-based organometallic single-site catalyst for CO2 -to-HCO2 - in aqueous medium, extremely high activity with a single-run turnover number (TON) up to 50816 was achieved which is the highest so far considering all the heterogeneous catalysts for this reaction in water. Additionally, the catalyst featured excellent reusability furnishing a cumulative TON of 285400 in 10 cycles with just 1.6 % loss in activity per cycle. Overall, the new catalyst displayed attributes that are important for developing tangible catalysts for practical applications.

Annulation-Induced Hidden Reactivity of the 1,2,4-Triazole Backbone.

Triazoles are an important class of compounds with widespread applications. Functionalization of the triazole backbone is thus of significant interest. In comparison to 1,2,3-triazoles, C-H activation-functionalization of the congeners 1,2,4-triazoles is surprisingly underdeveloped. Indeed, no such C-H activation-functionalization has been reported for 4-substituted 1,2,4-triazole cores. Furthermore, although denitrogenative ring-opening of 1,2,3-triazoles is well-explored, 1,2,4-triazole/triazolium substrates have not been known to exhibit N-N bond-cleaving ring-opening reactivity so far. In this work, we unveiled an unusual hidden reactivity of the 1,2,4-triazole backbone involving the elusive N-N bond-cleaving ring-opening reaction. This new reactivity was induced by a Satoh-Miura-type C-H activation-annulation at the 1,2,4-triazole motif appended with a pyridine directing group. This unique reaction allowed ready access to a novel class of unsymmetrically substituted 2,2'-dipyridylamines, with one pyridine ring fully-substituted with alkyl groups. The unsymmetrical 2,2'-dipyridylamines were utilized to access unsymmetrical boron-aza-dipyridylmethene fluorescent dyes. Empowered with desirable optical/physical properties such as large Stokes shifts and suitable hydrophobicity arising from optimal alkyl chain length at the fully-substituted pyridine-ring, these dyes were used for intracellular lipid droplet-selective imaging studies, which provided useful information toward designing suitable lipid droplet-selective imaging probes for biomedical applications.

Metal-Terpyridine Assembled Functional Materials for Electrochromic, Catalytic and Environmental Applications.

Molecular assembly induced by metal-terpyridine-based coordinative interactions has become an emergent research topic due to its ease of synthesis and diverse applications. This article highlights recent significant developments in the metal-terpyridine-based supramolecular architectures. At first, the design aspect of the molecular building blocks has been described, followed by elaboration on how the ligand backbone plays an important role for achieving different dimensionalities of the resulting assemblies which exhibit a wide range of potential applications. After that, we discussed different synthetic approaches for constructing these assemblies, and finally, we focused on their significant developments in three specific areas, viz., electrochromic materials, catalysis and a new application in wastewater treatment. In the field of electrochromic materials, these assemblies made important advancements in various aspects like sub-second switching time (<1 s), low switching voltage (<1 V), increased switching stability (>10000 cycles), tuning of multiple colors by using multimetallic systems, fabrication of charge storing electrochromic devices, utilizing and storing solar energy etc. Similarly, the catalysis field witnessed application of the metal-terpyridine assemblies in C-H monohalogenation, heterogeneous Suzuki-Miyaura coupling, photocatalysis, reduction of carbon dioxide, etc. Finally, the environmental application of these coordination assemblies includes capturing Cr(VI) from waste water efficiently with high capture capacity, good recyclability, wide pH independency etc.

Emerging Implications of the Concept of Hydricity in Energy-Relevant Catalytic Processes.

The "hydricity" of a species refers to its hydride-donor ability. Similar to how the pKa is useful for determining the extent of dissociation of an acid, the hydricity plays a vital role in understanding hydride-transfer reactions. A large number of transition-metal-catalyzed processes involve the hydride-transfer reaction as a key step. Among these, two key reactions-proton reduction to evolve H2 and hydride transfer to CO2 to generate formate/formic acid-represent a promising solution to build a sustainable and fossil-fuel-free energy economy. Therefore, it is imperative to develop an in-depth relationship between the hydricity of transition-metal hydrides and its influencing factors, so that efficient and suitable hydride-transfer catalysts can be designed. Moreover, such profound knowledge can also help in improving existing catalysts, in terms of their efficiency and working mechanism. With this broad aim in mind, some important research has been explored in this area in recent times. This Minireview emphasizes the conceptual approaches developed thus far, to tune and apply the hydricity parameter of transition-metal hydrides for efficient H2 evolution and CO2 reduction/hydrogenation catalysis focusing on the guiding principles for future research in this direction.

Reduction of Carbon Dioxide with Ammonia-Borane under Ambient Conditions: Maneuvering a Catalytic Way.

In the development of alternatives to the traditional catalytic hydrogenation of CO2 with gaseous H2, employing nongaseous H2 storage compounds as potential reductants for catalytic transfer hydrogenation of CO2 is promising. Ammonia-borane, due to its high hydrogen storage capacity (19.6 wt %), has been used for catalytic transfer hydrogenation of several organic unsaturated compounds. However, a similar protocol involving catalytic transfer hydrogenation of less reactive CO2 with NH3BH3 is yet to be realized experimentally. Herein, we demonstrate the first catalytic CO2 transfer hydrogenation process for generating formate salt with NH3BH3 under ambient conditions (1 atm and 30 °C) employing a cationic "Ir(III)-abnormal NHC" catalyst via an electrophilic NH3BH3 activation route. It exhibited an initial turnover frequency of 686 h-1 and a high turnover number (TON) of ≈1300 in just 4 h. Most significantly, the catalyst was durable enough to maintain long-term activity, and upon only periodic recharging of NH3BH3, it furnished a total TON of >4200 in 10 h.

Remote Terpyridine Integrated NHC-IrIII Luminophores as Potential Dual-Emissive Ratiometric O2 Probes.

A new class of bi-luminophoric dyad has been designed, consisting of an oxygen-sensitive phosphorescent NHC-IrIII center with a remotely integrated oxygen-insensitive fluorescent terpyridine unit. The new terpyridine flurophore-integrated NHC-IrIII molecule was demonstrated as a potential ratiometric O2 probe with built-in internal reference, exhibiting tunable dual-emissive features, as well as highly linear and reversible O2 -response behavior.

Switching of Reaction Pathway from C-C Rollover to C-N Ring-Extension Annulation.

This work discloses that a simple change in the anion of a copper(II) reagent along with the reaction solvent can dramatically alter the course of a Cp*RhIII -catalyzed C-H activation-annulation reaction leading to completely switchable chemoselective products. The nature of the anion in terms of its coordinating ability and basicity, and also the polarity of the solvent have been found to be the crucial factors in the observed divergence.

Heli(aza)cene: A Helical Molecular Tweezer with Tunable Intra- and Intermolecular Charge Transfer.

Non-planar fluorophores offer unique avenues of intra- and intermolecular energy transfer not available in their planar counterparts. We have rationally designed a molecular tweezer based on the pyridine-2,6-dicarboxamide framework having two structurally similar arms with extended π-surface. We termed this molecular tweezer as Heli(aza)cene (HAC) due to its spontaneous adoption of helical conformation stabilized by the amide and imine moieties present in it. In the helical conformation, the two arms of HAC are twisted unequally. This asymmetry confers dissimilar electronic character to the two arms and results in intramolecular charge transfer interactions in HAC. Homochiral stacking of the P- and the M- helices in crystal, and profound redshifting of the emission at higher concentrations of HAC was attributed to intermolecular charge-transfer interactions in aggregated/crystal state. Exposure of HAC, in solution as well as in the solid state, to Lewis/Brønsted acids results in rapid and vibrant color changes. This is the first example of a π-layered helical molecule exhibiting tunable intra-/intermolecular charge-transfer characteristics.

Small "Yaw" Angles, Large "Bite" Angles and an Electron-Rich Metal: Revealing a Stereoelectronic Synergy To Enhance Hydride-Transfer Activity.

Cyclometalated complexes are an important class of (pre)catalysts in many reactions including hydride transfer. The ring size of such complexes could therefore be a relevant aspect to consider while modulating their catalytic activity. However, any correlation between the cyclometalating ring size and the catalytic activity should be drawn by careful assessment of the pertinent geometrical parameters, and overall electronic effects thereof. In this study, we investigated the vital role of key stereoelectronic functions of two classes of iridacyclic complexes-five-membered and six-membered cycles-in manupulating the catalytic efficiency in a model hydride-transfer reaction. Our investigation revealed that there exists an interesting multidimensional synergy among all the relevant stereoelectronic factors-yaw angle, bite angle, and the electronic properties of both the ligand and the metal center-that governs the hydride donor ability (hydricity) of the complexes during catalysis. Thus the six-membered chelate complexes with small yaw and large bite angles, strong donor ligand, and electron-rich metal were found to be better catalysts than their five-membered analogues. A frontier molecular orbital analysis supported the significant role of the above stereoelectronic synergistic effect associated with the chelate ring to control the hydride donor ability of the complexes.

Switch in Catalyst State: Single Bifunctional Bi-state Catalyst for Two Different Reactions.

Disclosed here is a molecular switch which responds to acid-base stimuli and serves as a bi-state catalyst for two different reactions. The two states of the switch serve as a highly active and poorly active catalyst for two catalytic reactions (namely a hydrogenation and a dehydrogenative coupling) but in a complementary manner. The system was used in an assisted tandem catalysis set-up involving dehydrogenative coupling of an amine and then hydrogenation of the resulting imine product by switching between the respective states of the catalyst.

A phosphine-free molecularly-defined Ni(II) complex in catalytic hydrogenation of CO2.

The development of base metal catalysts capable of CO2 hydrogenation is a challenge and a necessity to progress from the scarce noble metal catalysts. In this regard, we report herein the first non-phosphine-based Ni complex, supported by a "carbazolato-bis-NHC" pincer ligand framework, for efficient catalytic hydrogenation of CO2 to formate. A tailored combination of the Ni complex as a catalyst, DBU as a base, and Zn(OAc)2 as an additive offered enhanced activity leading to a TON up to 5476 and an excellent yield up to 92% for the formate product from a reaction on ∼27 mmol scale.

Annulated oxazolium anion-π+ AIEgens.

A new class of anion-π+ AIEgens based on ring-fused annulated oxazolium architectures is reported, which can be readily synthesized via a single-step dual C-H activation annulative π-extension (APEX) protocol from simple oxazolium salts. The crucial and decisive role of anion-π+ interactions in their solid-state structural arrangement was analyzed to correlate their tunable AIE features and solid-state quantum yields.

Conformationally flexible heterohelicenes as stimuli-controlled soft molecular springs.

Structurally engineered molecules which can behave as stimuli-controlled mechanical nanomachines such as molecular shuttles, rotors, ratchets, and springs are important in several research areas, including molecular robotics, actuation, sensing, cargo transportation, etc. Helicenes, by virtue of their unique screw-type structures, were proposed as functional models for molecular springs; however, experimental realization has remained an elusive and unmet task until now, because of the lack of appropriate helicene molecules consisting of backbone-decorated dynamic architectures. Aiming to explore this unearthed direction, we present herein a novel class of modular flexible heterohelicenes with a stimuli (acid/base and light)-responsive core and peripheral modules. By applying pH (at core-embedded free imidazole sites) and light (at backbone-tethered dithienylethene units) stimuli, we demonstrate that these flexible heterohelicenes exhibit spring-like movement, with the reversible contraction/extension of the helical pitch. The uniquely functionalized structure of these molecules played a critical role in bestowing such capability, as revealed by crystallographic, spectroscopic and computational data. Careful assessment disclosed that the protonation/deprotonation-induced reversible generation and delocalization of positive charge throughout the π-conjugated helical rim switch the operative interactions between the π clouds of the terminal overlapping arene rings of the helicenes between repulsive and attractive, leading to extension/contraction of the helical pitch. On the other hand, in the case of the light stimulus, it was analyzed that the light-induced ring-closure of the photoactive dithienylethene units created a geometric distortion causing the helicenic wings to bend outward from the helicene rim, which resulted in extension of the helical pitch. The photo-assisted (or thermal) reverse ring-opening reaction converted the system to its original conformation, thus enabling the helicene molecule to display spring-like reversible extension/contraction motion. The new insights on the reversible dynamic features of this class of heterohelicenes under the influence of external stress would guide crucial design principles of helicene-based molecular springs for potential applications.

An all-aqueous and phosphine-free integrated amine-assisted CO2 capture and catalytic conversion to formic acid.

A phosphine-free Ir(III)-NHC-based efficient catalytic system is developed for integrated CO2 capture with tetramethylguanidine as a capturing agent and conversion to formate with H2 gas, conducting both the steps in water, affording product yield up to 85% and TON up to 19 171 in just 12 h. In the segment of "integrated CO2-capture and conversion to formate", this system represents not only the first phosphine-free module, but also one of the few best known homogeneous catalysts.