Bond Chemistry Research Articles

The Jekyll-and-Hyde electron transfer chemistry of hydrogen bonds.

The Jekyll-and-Hyde electron transfer chemistry of hydrogen bonds.

Synthesis and Reactivity of an Alumanyl-Tin Species to Form an Al,N-Heteroallene Derivative.

The molecular chemistry of metal-metal bonds is crucial for understanding the bonding and reactivity of metal-containing molecules as well as solid metals and their alloys, especially with respect to their application as catalysts for organic transformations and industrial processes. Despite the high efficiency of the recently developed nucleophilic alumanyl anions in the synthesis of diverse Al-metal bonds, the bonding between main group metals in a low oxidation state and the Al atom remains largely unexplored. This paper describes the reaction of an alumanyl anion with a chlorostannylene precursor to afford a compound with an unprecedented covalent Al-Sn bond. The lability of the covalent Al-Sn bond renders it reactive toward the insertion of carbodiimide, N2O, and phenylacetylene. Remarkably, the reaction with benzonitrile furnished an unprecedented Al,N-heteroallene species that contains a linear Al═N═C linkage.

Coordination and Hydrogen Bond Chemistry in Tungsten Oxide@Polyaniline Composite toward High-Capacity Aqueous Ammonium Storage.

Aqueous ammonium ion batteries (AAIBs) have garnered significant attention due to their unique energy storage mechanism. However, their progress is hindered by the relatively low capacities of NH4 + host materials. Herein, the study proposes an electrodeposited tungsten oxide@polyaniline (WOx@PANI) composite electrode as a NH4 + host, which achieves an ultrahigh capacity of 280.3 mAh g-1 at 1 A g-1, surpassing the vast majority of previously reported NH4 + host materials. The synergistic interaction of coordination chemistry and hydrogen bond chemistry between the WOx and PANI enhances the charge storage capacity. Experimental results indicate that the strong interfacial coordination bonding (N: →W6+) effectively modulates the chemical environment of W atoms, enhances the protonation level of PANI, and thus consequently the conductivity and stability of the composites. Spectroscopy analysis further reveals a unique NH4 +/H+ co-insertion mechanism, in which the interfacial hydrogen bond network (N-H···O) accelerates proton involvement in the energy storage process and activates the Grotthuss hopping conduction of H+ between the hydrated tungsten oxide layers. This work opens a new avenue to achieving high-capacity NH4 + storage through interfacial chemistry interactions, overcoming the capacity limitations of NH4 + host materials for aqueous energy storage.

Masking Strategy Constructed Metal Coordination Hydrogels with Improved Mechanical Properties for Flexible Electronic Sensors.

Metal coordination hydrogels (MC-HGs) that introduce dynamically coordinate bonds together with metal ionic conduction have attracted considerable attention in flexible electronics. However, the traditional soaking method alleged to have technical scalability faces the challenge of forming MC-HGs with a "core-shell" structure, which undoubtedly reduces the whole mechanical properties and ionic stimulation responsiveness required for flexible electronics materials. Herein, a novel strategy referred to as "masking" has been proposed based on the theory of the valence bond and coordination chemistry. By regulating the masking agents and their concentrations as well as pairing mode with the metal ions, the whole mechanical properties of the resulting composites (MC-HGsMasking) show nearly double the values of their traditional soaking samples (MC-HGsSoaking). For example, the fracture stress and toughness of Fe-HGsMasking(SA,5.0g/L) are 1.55 MPa and 2.14 MJ/m3, almost twice those of Fe-HGsSoaking (0.83 MPa and 0.93 MJ/m3, respectively). Microstructure characterization combined with finite element analysis, molecular dynamics, and first-principles simulations demonstrates that the masking strategy first facilitating interfacial permeation of metal complexes and then effective coordination with functional ligands (carboxylates) of the hydrogels is the mechanism to strengthen the mechanical properties of composites MC-HGsMasking, which has the potential to break through the limitations of current MC-HGs in flexible electronic sensor applications.

A Short-Range Ordered α-MoO3 with Modulated Interlayer Structure via Hydrogen Bond Chemistry for NH4 + Storage.

The layered orthorhombic molybdenum trioxide (α-MoO3) is a promising host material for NH4 + storage. But its electrochemical performances are still unsatisfactory due to the absence of fundamental understanding on the relationship between structure and property. Herein, NH4 + storage properties of α-MoO3 are elaborately studied. Electrochemistry together with ex situ physical characterizations uncoverthat irreversible H+/NH4 + co-intercalation in the initial cycle confines the electrochemically reactive domain to the near surface of α-MoO3 thus resulting in a low reversible NH4 + storage capacity. This issue can be resolved by decreasing ion diffusion pathway to construct short-range ordered α-MoO3 (SMO), which improves the specific capacity to 185 mAh g-1. SMO suffers from dissolution issue. In view of this the interlayer structure of SMO is reconstructed via hydrogen bond chemistry to reinforce the structural stability and it is discovered that the hydrogen bond network only with moderate intensity endows SMO with both high capacity and ability against dissolution. This work presents a new avenue to improve the NH4 + storage properties of α-MoO3 and highlights the important role of hydrogen bond intensity in optimizing electrochemical properties.

Hydrophilic carbon-carbon covalent linkage network structure for strong acid/alkali resistant and antifouling nanofiltration membrane

The nanofiltration (NF) membrane plays a crucial role in wastewater treatment by separating ions and molecules. However, traditional polyamide (PA) thin-film composite (TFC) NF membranes have limitations in durability under acidic or alkaline conditions and are prone to fouling, which limits their applications and increases costs. In this study, we have successfully developed a new nanofiltration membrane with an active layer composed of hydrophilic carbon-carbon covalent bond linkage network through UV irradiation-initiated polymerization of a kind of sulfobetaine - [2-(methacryloyloxy)ethyl]dimethyl-(3-sulfopropyl) ammonium hydroxide (DMAPS) - or acrylic acid (AA) on the surface of poly (ether sulfone) (PES) substrate. The carbon-carbon covalent bond (C–C) chemistry used in the preparation of the NF membrane results in exceptional durability towards acid and base, enabling it to maintain its ion separation efficiency (up to 94.2 % and 90.3 % of the initial Na2SO4 rejections) under strong acidic (20 % (w/v) H2SO4) and strong alkaline (2 M NaOH) conditions. Additionally, the water-attracting nature of polyDMAPS and PAA effectively prevents the fouling of protein and bacteria on the NF membrane surface. This breakthrough in manufacturing NF membranes significantly improves their environmental durability, making them suitable for use in highly acidic or alkaline environments (e.g., pH < 0 and pH > 14), including heavily contaminated ones.

Stable WO3 electrochromic system based on NH4+ hydrogen bond chemistry

As the best-known and extensively-studied electrochromic material, tungsten trioxide (WO3) has drawn tremendous interest due to its low material cost, environmental benignity, dual band regulation, high optical modulation, and high chemical stability. However, these films always suffer from ion-trapping-induced degradation in electrochromic performance when cycled in alkali cation (such as Li+, Na+, K+, etc.) electrolytes. Herein, we report a stable WO3 electrochromic system enabled by a NH4CF3SO3-TEP (Triethyl phosphate) organic electrolyte. Based on comparative experiments and systematic characterizations, the prolonged cycling stability is mainly attributed to the formation of hydrogen bonds between the NH4+ ions and the WO3 lattice, which are much weaker than metallic coordination bonds. Furthermore, the bulky CF3SO3− anion and large TEP solvent molecule are also favorable to stabilize WO3, since they are more resistive to be co-inserted into the WO3 lattice along with the shuttling NH4+ cations. Thanks to these merits, this NH4CF3SO3-TEP electrolyte simultaneously enables great electrochromic activity (76.1 % transmittance modulating ability at 633 nm) and impressive cyclic color-switching stability (1000 times color change without any detectable electrochromic performance or mechanical degradation), overwhelmingly outperforming the conventional Li+/K+ electrolytes. Furthermore, as a demonstration of its application, a WO3/Zn electrochromic device is fabricated based on a NH4+/Zn2+-CF3SO3 dual-cation TEP electrolyte. These findings may shed light on the in-depth understanding of WO3′s “ion trapping” effect, as well as the electrolyte design of high-performance WO3-based electrochromic devices.

Structure, bond chemistry and enhanced microwave dielectric properties of La2−xYxMo2O9 ceramics with low sintering temperature

Low-temperature sintered La2−xYxMo2O9 ceramics (x = 0–0.12) were synthesized by solid-state method. XRD analysis confirmed pure La2Mo2O9 with a cubic structure (space group P 21 3). Sintering at 925 °C resulted in La2Mo2O9 ceramic with favorable microwave dielectric properties: εr = 17.8, Q × f = 24300 GHz, τf = −35.1 ppm/°C. Notably, adding Y3+ greatly improved Q × f and τf. Sintering La1.88Y0.12Mo2O9 at 900 °C significantly enhanced microwave dielectric properties: εr = 17.4, Q × f = 34100 GHz, τf = −5.5 ppm/°C. εr was primarily influenced by ionic polarizability, while Q × f correlated positively with packing fraction. Analysis based on P-V-L theory showed that increased ionicity, lattice energy, and bond energy led to higher εr, Q × f, and τf values. Raman spectroscopy revealed that most observed peaks were associated with Mo-O bond vibrations. These findings highlight La2−xYxMo2O9 ceramics as promising candidates for LTCC materials.

A Quantum-Chemical Bonding Database for Solid-State Materials

An in-depth insight into the chemistry and nature of the individual chemical bonds is essential for understanding materials. Bonding analysis is thus expected to provide important features for large-scale data analysis and machine learning of material properties. Such chemical bonding information can be computed using the LOBSTER software package, which post-processes modern density functional theory data by projecting the plane wave-based wave functions onto an atomic orbital basis. With the help of a fully automatic workflow, the VASP and LOBSTER software packages are used to generate the data. We then perform bonding analyses on 1520 compounds (insulators and semiconductors) and provide the results as a database. The projected densities of states and bonding indicators are benchmarked on standard density-functional theory computations and available heuristics, respectively. Lastly, we illustrate the predictive power of bonding descriptors by constructing a machine learning model for phononic properties, which shows an increase in prediction accuracies by 27% (mean absolute errors) compared to a benchmark model differing only by not relying on any quantum-chemical bonding features.

Supramolecular assembly guided by photolytic redox cycling

AbstractIn living systems, the formation of structures relies on balancing kinetic and thermodynamic influences powered by reversible covalent bond chemistry. Although synthetic efforts have replicated these processes to some extent, elucidating their combination is necessary to identify mechanisms that confer nature’s structural precision and flexibility within a complex environment. Here we design a photolytic reaction cascade where competing redox pathways control the transience, interconversion and production rates of thiol/disulfide supramolecular monomers in situ. In contrast to direct assembly by dissolution, cascade generation of the same monomers formed hierarchical assemblies with different structural order. Redox-induced cycling between thiol–disulfide formation led to the emergence of new secondary structures and chirality within the final assemblies. These multiple structural states found within the same molecular system demonstrate the concept of assembly plasticity engaged frequently in biology. We demonstrate the importance of reaction complexity in controlling supramolecular propagation and in expanding the library of nanoarchitectures that can be created.

Mechanically Interlocked Vitrimer Based on Polybenzoxazine and Polyrotaxane

A mechanically interlocked vitrimer (MIV) based on a benzoxazine monomer and polyrotaxane (PR) has been prepared through a mechanically interlocked network (MIN) and dynamic covalent bond chemistry. The dynamic transacetalation exchange through the N,O-acetal-type polybenzoxazine (PBz) structure was catalyzed by a tin compound. Compared to the controlled PBz vitrimer without a MIN, the designed PBz MIV shows enhanced mechanical performance including ductility and tensile strength while maintaining relatively high Young’s modulus and glass transition temperature (Tg). The PBz MIV can be reprocessed several times without compromising mechanical performance and thermal stability. The PBz MIV also exhibits a faster dynamic bond exchange and a lower activation energy compared to the controlled PBz vitrimer due to the mobile intramolecular motions of PR in the network allowing for a dynamic bond exchange in the MIV more readily. The usefulness of the present study for the preparation of high-performance eco-friendly thermosetting vitrimers is discussed.

Phosphate Ester Bond Chemistry with Zirconium (IV) Catalysts

Earth’s infancy was a time of immense chemical complexity. Over many millions of years, steady chemical cycles were formed and driven by thermodynamics and organic precursors left over from the planet’s formation. In aqueous environments, this chemistry may have led to the formation of catalytic RNA species capable of information storage and replication. Presumably, the formation of these oligonucleotides was catalyzed by primordial Earth’s abundant mineral content. However, the species that accelerated these types of transformations are unknown. In this study, the role of Zr+4 in the catalytic formation of phosphate ester bonds was explored. Through TLC screening, it was found that most of the test conditions produced no observable phosphorylated products. In the final samples, there were highly polar spots which may have contained phosphate-bearing compounds. These findings provide mixed certainty about zirconium’s catalytic capacity for ester formation but suggest that zirconium metal organic frameworks (MOFs) and alternative metal ions may be viable routes for future investigation. Lay Summary Earth began as a planet of rock and magma, hardly recognizable without the biological adornments that characterize it today. For nearly a billion years, consistent comet and asteroid impacts heated the planet and vaporized any reservoirs of water or organic matter that covered the surface. As this bombardment subsided, life came to fruition in half the time that the mineral rain had lasted. The question of how this transition occurred is one of the most elusive in the biochemical field. In particular, it is still unknown how all life, whether primordial or modern, came to share polynucleotides as an essential coding system for all their requisite biological functions. This study explored the role of Zr+4, an abundant mineral on early Earth, in the catalytic formation of phosphate ester bonds, the core linkages in DNA and RNA. Through TLC screening, it was found that most of the test conditions produced no observable phosphorylated products. In the final samples, highly polar spots may have contained phosphate-bearing compounds. These findings provide mixed certainty about zirconium’s capacity for ester formation but suggest that zirconium metal-organic frameworks (MOFs) and alternative metal ions that reflect early Earth’s composition may be viable routes for future investigation into this grand mystery. To see the complete thesis, please visit https://scholar.colorado.edu/concern/undergraduate_honors_theses/cf95jc857.

Complexes Featuring a cis-[M U M] Core (M=Rh, Ir): A New Route to Uranium-Metal Multiple Bonds.

Although examples of multiple bonds between actinide elements and main-group elements are quite common, studies of the multiple bonds between actinide elements and transition metals are extremely rare owing to difficulties associated with their synthesis. Here we report the first example of molecular uranium complexes featuring a cis-[M U M] core (M=Rh, Ir), which exhibits an unprecedented arrangement of two M U double dative bond linkages to a single U center. These complexes were prepared by the reactions of chlorine-bridged heterometallic complexes [{U{N(CH3 )(CH2 CH2 NPi Pr2 )2 }(Cl)2 [(μ-Cl)M(COD)]2 }] (M=Rh, Ir) with MeMgBr or MeLi, a new method for the construction of species with U-M multiple bonds. Theoretical calculations including dispersion confirmed the presence of two U M double dative bonds in these complexes. This study not only enriches the U M multiple bond chemistry, but also provides a new opportunity to explore the bonding of actinide elements.

Complexes Featuring a cis‐[MUM] Core (M=Rh, Ir): A New Route to Uranium‐Metal Multiple Bonds

AbstractAlthough examples of multiple bonds between actinide elements and main‐group elements are quite common, studies of the multiple bonds between actinide elements and transition metals are extremely rare owing to difficulties associated with their synthesis. Here we report the first example of molecular uranium complexes featuring a cis‐[M U M] core (M=Rh, Ir), which exhibits an unprecedented arrangement of two M U double dative bond linkages to a single U center. These complexes were prepared by the reactions of chlorine‐bridged heterometallic complexes [{U{N(CH3)(CH2CH2NPiPr2)2}(Cl)2[(μ‐Cl)M(COD)]2}] (M=Rh, Ir) with MeMgBr or MeLi, a new method for the construction of species with U−M multiple bonds. Theoretical calculations including dispersion confirmed the presence of two U M double dative bonds in these complexes. This study not only enriches the U M multiple bond chemistry, but also provides a new opportunity to explore the bonding of actinide elements.

A simple, sensitive, label-free electrochemical immunosensor based on the chitosan-coated silver/cerium oxide (CS@Ag/CeO2) nanocomposites for the detection of alpha-fetoprotein (AFP)

Metal oxide-based sensors have the benefit of inexpensive, quick response, and high sensitivity in detecting specific biological species. In this article, a simple electrochemical immunosensor was fabricated using antibody-chitosan coated silver/cerium oxide (Ab-CS@Ag/CeO2) nanocomposites on a gold electrode for sensitive alpha-fetoprotein (AFP) diagnosis in human serum samples. Successfully synthesis of AFP antibody-CS@Ag/CeO2 conjugates was confirmed through Fourier transform infrared spectra of the prototype. The amine coupling bond chemistry was then used to immobilize the resultant conjugate on a gold electrode surface. It was observed that the interaction of the synthesized Ab-CS@Ag/CeO2 nanocomposites with AFP prevented an electron transfer and reduced the voltammetric Fe(CN)6 3−/4− peak current, which was proportional to the amount of AFP. The linear ranges of AFP concentration were found from 10−12–10−6 g.ml−1. The limit of detection was calculated using the calibration curve and came out to be 0.57 pg.ml−1. The designed label-free immunosensor successfully detected AFP in human serum samples. As a result, the resulting immunosensor is a promising sensor plate form for AFP detection and could be used in clinical bioanalysis.

Imparting Reprocessability, Quadruple Shape Memory, Self-Healing, and Vibration Damping Characteristics to a Thermosetting Poly(urethane-urea)

The advent of dynamic covalent bond chemistry (DCBC) has sparked renewed research interest in reprocessability of thermosetting polymers. However, combining reprocessability with stimuli-responsiveness remains a challenge for futuristic applications. Usually, a combination of complementary DCBCs is employed to integrate reprocessability with shape memory as well as self-healing (SH) attributes in a single polymeric system. In the present work, we report two-component poly(urethane-urea) (PUU) networks, with varied hard segment (HS) concentrations, that exhibit quadruple shape memory (QSM), efficacious vibration damping, thermally activated intrinsic SH as well as multiple cycles of thermal reprocessability. The component A is an isocyanate capped bi-soft segment blend of polybutadiene diol and polypropylene glycol, while the second component comprises an aromatic diamine chain extender solubilized in an oligomeric polyoxypropylene triol. The networks characterized through FTIR as well as small- and wide-angle X-ray scattering (SAXS and WAXD) revealed a phase-separated morphology with extensive hydrogen-bonding (H-bonding) interactions in the HS domains of the PUU networks. Dynamic mechanical analysis (DMA) measurements revealed broad dissipation factor (tan δ) vs temperature and frequency profiles of the networks, which could be leveraged for efficacious passive vibration damping applications. A dissociative mechanism of urethane and urea bond exchange, evidenced from temperature-dependent FTIR studies enabling facile stress relaxation, is proposed to be the mechanistic origin of the reprocessability and SH of the networks. A broad dissipation factor (tan δ) vs temperature profiles endowed the networks with QSM characteristics. We posit that the study is relevant for expanding the scope of DCBCs for development of reprocessable thermosetting polyurethanes with multiple smart functionalities.

USc2C2 and USc2NC Clusters with U-C Triple Bond Character Stabilized Inside Fullerene Cages.

The chemistry of f-block metal-carbon multiple bonds is underdeveloped compared to well-established carbene complexes of the d-block transition metals. Herein, we report two new actinide-rare earth mixed metal carbides and nitrogen carbide cluster fullerenes, USc2C2@D5h(6)-C80 and USc2NC@D5h(6)-C80, which contain U-C bonds with triple bond character and were successfully synthesized and characterized by mass spectrometry, UV-vis-NIR spectroscopy, Fourier transform infrared spectroscopy, single crystal X-ray diffraction, and DFT calculations. Crystallographic studies show that the two previously unreported clusters, USc2C2 and USc2NC, are stabilized in the D5h(6)-C80 carbon cage and adopt unique trifoliate configurations, in which C2/NC units are almost vertically inserted into the plane defined by the U and two Sc atoms. Combined experimental and theoretical studies further reveal the bonding structure of USc2C2 and USc2NC, which contain C═U(VI)═C and C═U(V)═N bonding motifs. The electronic structures of the two compounds are determined as U6+(Sc2)6+(C4-)2@D5h(6)-C804- and U5+(Sc2)6+(N)3-(C)4-@D5h(6)-C804-, respectively. Quantum-chemical studies confirm that the U-C bonds in both molecules show unprecedented multicenter triple-bond character. The discovery of this unique U-C multiple bond offers a deeper understanding of the fundamentals of uranium chemistry.

Surface Oxygen Coordination of Hydrogen Bond Chemistry for Aqueous Ammonium Ion Hybrid Supercapacitor

AbstractAqueous ammonium ion hybrid supercapacitor (A‐HSC) combines the charge storage mechanisms of surface adsorption and bulk intercalation, making it a low‐cost, safe, and sustainable energy storage candidate. However, its development is hindered by the low capacity and unclear charge storage fundamentals. Here, the strategy of phosphate ion‐assisted surface functionalization is used to increase the ammonium ion storage capacity of an α‐MoO3 electrode. Moreover, the understanding of charge storage mechanisms via structural characterization, electrochemical analysis, and theoretical calculation is advanced. It is shown that NH4+ intercalation into layered α‐MoO3 is not dominant in the A‐HSC system; rather, the charge storage mainly depends on the adsorption energy of surface “O” to NH4+. It is further revealed that the hydrogen bond chemistry of the coordination between “O” of surface phosphate ion and NH4+ is the reason for the capacity increase of MoO3. This study not only advances the basic understanding of rechargeable aqueous A‐HSC but also demonstrates the promising future of surface engineering strategies for energy storage devices.

Bifunctional Fluorinated Anthraquinone Additive for Improving Kinetics and Interfacial Chemistry in Rechargeable Li–S Batteries

The uncontrollable Li deposition and severe lithium polysulfide (LiPS) shuttling hinder the commercial application in lithium–sulfur (Li–S) batteries. Here, we propose a bifunctional electrolyte additive, 1,4-difluoroanthraquinone (DFAQ), to be used for lithium regulation and acceleration of sulfur redox kinetics. DFAQ is conducive to form a rigid and smooth LiF-rich organic–inorganic hybrid solid electrolyte interphase (SEI), realizing reversible Li plating/stripping, restraining dendrite growth, and shielding Li anode from the detrimental side reaction with LiPSs. More importantly, DFAQ can be used as a redox mediator to enable an oxygen radical-mediated catalytic cycle to dramatically promote the conversion of LiPSs. Accordingly, the Li–S battery with DFAQ demonstrates ultrahigh discharge capacities, enhanced high-rate performance, and outstanding long-cycle stability (1693.4 mAh g–1 at 0.5C over 700 cycles). Even under harsh conditions including high sulfur loading (5.8 mgS cm–2), ultrathin Li anode (50 μm), and low E/S ratio (5.0 μL mgS–1), the Li–S battery with DFAQ shows 80 cycles in comparison to just 30 cycles for control battery. This work demonstrates a facile additive strategy originated from bond chemistry to build applicable Li–S batteries.

Raman Spectroscopy Reveals Phase Separation in Imine-Based Covalent Adaptable Networks.

The introduction of dynamic covalent bonds into cross-linked polymer networks enables the development of strong and tough materials that can still be recycled or repurposed in a sustainable manner. To achieve the full potential of these covalent adaptable networks (CANs), it is essential to understand-and control-the underlying chemistry and physics of the dynamic covalent bonds that undergo bond exchange reactions in the network. In particular, understanding the structure of the network architecture that is assembled dynamically in a CAN is crucial, as exchange processes within this network will dictate the dynamic-mechanical material properties. In this context, the introduction of phase separation in different network hierarchies has been proposed as a useful handle to control or improve the material properties of CANs. Here we report-for the first time-how Raman confocal microscopy can be used to visualize phase separation in imine-based CANs on the scale of several micrometers. Independently, atomic force microscopy (AFM) confirmed the phase-separated domains inside the polymer. Remarkably, the materials were found to undergo phase separation despite being built up from miscible monomers, which arguably should yield homogeneous materials. We found that the phase separation not only affected the appearance of the material but-more notably-also had a noticeable effect on the thermal-mechanical properties of the material: CANs (of equal aliphatic/aromatic monomer composition) that displayed phase separation had both a higher crossover temperature (T cross, where tan(δ) = 1, and where the material transits from a rubbery to a viscous state) and an increased elastic modulus (G'). By modifying the CAN architecture, we were able to either suppress or enhance the phase separation, and we propose that the phase separation is driven by favorable π-π interactions between the aromatic components. Our work further shows the importance of phase separation in CANs, including in networks built from miscible components, and provides a handle to control the dynamic material properties. Moreover, our work underlines the suitability of Raman imaging as a method to visualize phase separation in CANs.