Quadruple Bond Research Articles

Self-healing flexible strain sensors based on dynamically cross-linked conductive nanocomposites

Self-healing, flexible, robust and adaptable strain sensors with intelligent skin-like features are greatly promising for future wearable devices. In this work, we demonstrate a self-healing flexible strain sensor with stretchability, robust mechanical strength, and high sensing sensitivity, which can monitor human motions. The sensor is constructed by the dynamically cross-linked conductive nanocomposite based on imine and quadruple hydrogen bonds. Due to the reversible interactions, the nanocomposites exhibit excellent self-healing performances with the healing efficiency up to 95%. The interfacial compatibility between the nanofillers and polymer networks is enhanced through the supramolecular interactions. Based on piezoresistive effects, the change of resistance for the nanocomposite-based strain sensor can be obviously observed under various deformation including stretching, bending, and twisting. Meanwhile, the gauge factor of the sensor reaches 46, showing high sensing sensitivity. Benefited from the self-healing feature, the sensor can withstand mechanical damage and restore the function of detecting human motions, enabling reliability and stability in practical applications, which shows great potential for developing smart wearable devices, healthcare monitoring, and human-machine interfaces.

The Spectroscopy of C2: A Cosmic Beacon.

ConspectusDicarbon, the molecule formed from two carbon atoms, is among the most abundant molecules in the universe. Said by some to exhibit a quadruple bond, it is bound by more than 6 eV and supports a large number of valence electronic states. It thus has a rich spectroscopy, with 19 one-photon band systems, four of which were discovered by the author and co-workers. Its spectrum was among the first to be described: Wollaston reported the emission spectra from blue flames in 1802.C2 is observed in a variety of astronomical objects, including stars, circumstellar shells, nebulae, comets and the interstellar medium. It is responsible for the green color of cometary comae but is not observed in the comet tail. It can be observed in absorption and emission by optical spectroscopy in the infrared, visible, and ultraviolet regions of the spectrum, and because it has no electric-dipole-allowed vibrational or rotational transitions, its spectral signature is a sensitive probe of the local environment.Before the work described in this Account, models of C2 photophysics included the thitherto-unobserved c3Σu+ state and parametrized the strength of spin-forbidden intercombination transitions. Furthermore, they did not account for photodissociation of C2, even though it was identified in the 1930s as a key process. Inspired by the observation of C2 in the Red Rectangle nebula, the author was motivated to instill rigor into C2 models and embarked on a spectroscopic and computational journey that has lasted 15 years.We were the first to identify the c3Σu+ state through the d3Πg-c3Σu+ transitions, which were to become known as the "Duck" system. This minor partner to the well-known Swan bands is a key part of astrophysical C2 models and can now be included with rigor. We identified the e3Πg-c3Σu+ system, and the c3Σu+ state is now well-studied. Meanwhile others described the singlet-triplet and triplet-quintet interactions in exquisite detail, allowing rigorous modeling of the a-X and c-X intercombination transitions.The final piece of the C2 puzzle would be understanding how long it survives before being broken into carbon atom fragments. Though predicted by Herzberg, predissociation in the e3Πg state had never been observed. To find it would require the complicated ultraviolet spectroscopy of C2 to be disentangled. In so doing, we identified the 43Πg and 33Πg states of C2, thus uncovering two new band systems. The 43Πg state allowed the first accurate determination of the ionization energy of C2. With these new band systems secure, we extracted new levels of the D1Σu+ state (Mulliken bands) and the e3Πg state (Fox-Herzberg bands) from our spectra. Upon climbing the energy ladder in the e3Πg state to v = 12, we finally identified the route to predissociation of C2 via non-adiabatic coupling to the d3Πg state. This observation provided the first laboratory evidence for why C2 is observed in the coma of a comet but not the tail.

Boron-boron quadruple bond in Li3B2- and Li4B2 clusters.

Homopolar quadruple bonding in first row p-block elements is expected due to the presence of four valence orbitals accessible for bonding. Although quadruple bonding in C2 has been proposed, no such proposal exists for B2. Here we report the unprecedented B-B quadruple bonding in Li3B2- and Li4B2 clusters based on high level theoretical calculations. The quadruple bonding is omnipresent in the global minimum, its nearest energy isomer and the transition states connecting them. Various bonding analyses reveal the unprecedented nature of the BB quadruple bonding interaction.

Is a transition metal-silicon quadruple bond viable?

Quadruple bonding in heavier main group elements is not known albeit having four valence orbitals accessible for bonding. Here we report the unprecedented quadruple bonding between a silicon atom and a transition metal fragment in the 1A1 electronic ground state of C3v symmetric SiRu(CO)3 based on high level theoretical calculations. Various bonding analyses reveal the nature of the Si[quadruple bond, length as m-dash]Ru quadruple bonding interaction, which involves one usual Si-Ru σ bond, two usual Si-Ru π bonds and one additional Si → Ru dative σ bond.

Recent developments: self-healing polymers based on quadruple hydrogen bonds

The microcrack of materials was inevitable in the process of transportation, storage and utilization, which may cause functional failure and resources waste. Inspired by nature, self-healing polymers have attracted significant attention owing to widespread applications in wearable electronics, cartilage replacement, coatings and elastomer. Compared with extrinsic healing, intrinsically healable polymers offer multiple self-healing by supramolecular reversible interactions, such as host-guest interactions, π-π stacking, ionic interactions and hydrogen-bonding. Self-healing polymers based on quadruple hydrogen bonds have been extensively investigated due to its high thermodynamic stability and rapid kinetic reversibility, and have been well developed for the past two decades. In this paper, the strategies and designs of self-repairing polymers based on quadruple hydrogen bond were classified and summarized, including main-chain self-healing polymers, side-chain self-healing polymers and supramolecular self-healing polymers. It is expected that quadruple hydrogen bonding can be construct more robust, highly tough, multi-stimuli-responsive, and fast self-healing supramolecular polymer, and is potential to be applied to numerous civilian and military fields in the future.

The role of the phosphorus lone pair in the low-energy binuclear phospholyl vanadium carbonyl structures: comparison with cyclopentadienyl analogues

The structures and energetics of the binuclear phospholyl vanadium carbonyls (C4H4P)2V2(CO)n (n = 7, 6, 5, 4, 3, 2, 1) have been investigated using density functional theory. The lowest energy heptacarbonyl (C4H4P)2V2(CO)7 structures resemble those of the dimanganese pentacarbonyl (C4H4P)2Mn2(CO)5 with one seven-electron donor bridging η5,η1-C4H4P ring and no direct vanadium–vanadium bond. Similarly, the lowest energy hexacarbonyl (C4H4P)2V2(CO)6 structure resembles that of the dimanganese tetracarbonyl (C4H4P)2Mn2(CO)4 with two seven-electron donor bridging η5,η1-C4H4P rings and no direct vanadium–vanadium bond. The lowest energy pentacarbonyl (C4H4P)2V2(CO)5 structure has terminal η5-C4H4P phospholyl rings and a formal V≡V triple bond of length ~ 2.45 A similar to the experimentally known and structurally characterized cyclopentadienyl analogue (η5-C5H5)2V2(CO)5. Various combinations of V=V double bonds or V≡V triple bonds, four-electron donor bridging carbonyl groups and seven-electron donor bridging η5,η1-C4H4P rings are found in the more highly unsaturated derivatives (C4H4P)2V2(CO)n (n = 4, 3, 2) to give 17- and 18-electron vanadium configurations for triplet- and singlet-state structures, respectively. Formal V≣V quadruple bonds are found only in the highly unsaturated lowest energy singlet (C4H4P)2V2(CO)n (n = 2, 1) structures, which, however, lie at somewhat higher energies than isomeric triplet structures.

Polyethylenes functionalized with ureidopyrimidone: synthesis, thermomechanical properties and shape memory behavior

In this contribution, we reported an approach to functionalize polyethylene with quadruple hydrogen bonds.

Towards photoswitchable quadruple hydrogen bonds via a reversible "photolocking" strategy for photocontrolled self-assembly.

Developing new photoswitchable noncovalent interaction motifs with controllable bonding affinity is crucial for the construction of photoresponsive supramolecular systems and materials. Here we describe a unique “photolocking” strategy for realizing photoswitchable control of quadruple hydrogen-bonding interactions on the basis of modifying the ureidopyrimidinone (UPy) module with an ortho-ester substituted azobenzene unit as the “photo-lock”. Upon light irradiation, the obtained Azo-UPy motif is capable of unlocking/locking the partial H-bonding sites of the UPy unit, leading to photoswitching between homo- and heteroquadruple hydrogen-bonded dimers, which has been further applied for the fabrication of novel tunable hydrogen bonded supramolecular systems. This “photolocking” strategy appears to be broadly applicable in the rational design and construction of other H-bonding motifs with sufficiently photoswitchable noncovalent interactions.

Application of a super-stretched self-healing elastomer based on methyl vinyl silicone rubber for wearable electronic sensors

A super-stretched self-healing elastomer for flexible electronic devices by introducing quadruple hydrogen bonds.

Chromous carbonates containing a square-grid layer of {Cr2(CO3)4}n4n- based on a dichromium(II,II) paddlewheel core.

Polymeric coordination compounds based on Cr2n+ paddle-wheel building blocks with non-carboxylate O,O-donor ligands chelating and bridging the Cr-Cr centers have been underexplored hitherto. This paper reports the synthesis and crystal structure of a new homo-valent chromium(ii,ii) compound, Na3HCr2(CO3)4·10H2O (1). It has a two-dimensional structure in which the paddlewheel chromium(ii,ii) units of Cr2(CO3)44- are cross-linked through the carbonate groups. The layers are stacked along the [100] direction, and Na ions fill the intra and interlayer spaces with a neighboring layer distance of about 11.3 Å. The investigation of the primary magnetic properties and theoretical studies with density functional theory (DFT) reveal the partial paramagnetic properties of compound 1 arising from the Boltzmann distribution between a ground state σ2π4δ2 with S = 0 and a low-lying excited state σ2π4δδ* with S = 1 for the Cr2(ii,ii) dimer. According to Raman spectra measurements combined with theoretical calculations, the two Raman bands in the small-wavenumber region at 335 and 297 cm-1 were assigned to the vibration of the Cr-O bonds and the band at 371 cm-1 was assigned to the stretching of the Cr-Cr quadruple bond.

Synthesis and stability of the dirhenium(III) cluster compounds with isoleucine, serine and proline in aqueous solutions

The previously developed methods for the synthesis of cis-tetrachlorodi--carboxylates of dirhenium(III) were modified, due to which the derivatives of Re26+ with proteinogenic amino acids (AA) isoleucine, serine and proline were synthesized for the first time. The composition and structure of these substances with the general formula cis-[Re2(АA)2Cl4(CH3CN)2]Cl2 were confirmed by elemental analysis, electron adsorption and IR spectroscopy. The presence of a characteristic peak, which corresponds to the *-electronic transition of the Re–Re quadruple bond for compounds with the cis-arrangement of two bridging-coordinated carboxylate groups in the ligand environment of the Re26+ cluster, was showed by using the data on the electronic absorption spectra of solutions of the synthesized compounds. The IR spectrum contains an intense, weakly split band in the region of 1466–1458 cm–1, which is attributed to the s(CO) coordinated carboxyl group and indicates its bridging coordination to the binuclear Re26+ fragment. The spectra exhibited the presence of bands of stretching (NH3+) and bending vibrations (NH3+) of protonated amino groups in complex compounds of isoleucine and serine and the presence of bands of stretching (NH2+) and bending vibrations (NH2+) of the protonated imino group of proline. The stability of the prepared complex compounds in aqueous solutions was investigated. It is shown that the hydrolysis of the synthesized substances occurs within 9–14 days with a decrease in the pH of the reaction solution due to a gradual replacement of labile chloride ligands by OH–-groups at the first stages of interaction with water. The resistance to hydrolysis is an important parameter of biologically active substances; the determination of the resistance to hydrolysis will expand understanding of the possible mechanisms of their specific biological activity.

The Synthesis, Bonding, and Transformation of a Ligand-Protected Gold Nanohydride Cluster.

Gold does not react with H2 to form bulk hydrides. Here we report the synthesis and characterization of a gold nanohydride protected by diphosphine ligands, [Au22 H4 (dppo)6 ]2+ [dppo=1,8-bis(diphenylphosphino)octane]. The Au22 core consists of two Au11 units bonded by eight Au atoms not coordinated by the diphosphine ligands. The four H atoms are found to bridge the eight uncoordinated Au atoms at the interface. Each Au11 unit can be viewed as a tetravalent superatom forming four delocalized Au-H-Au bonds, similar to the quadruple bond first discovered in the [Re2 Cl8 ]2- inorganic cluster. The [Au22 H4 (dppo)6 ]2+ nanohydride is found to lose H atoms over an extended time via H evolution (H2 ), proton (H+ ) and hydride (H- ) releases. This complete repertoire of H-related transformations suggests that the [Au22 H4 (dppo)6 ]2+ nanohydride is a versatile model catalyst for understanding the mechanisms of chemical reactions involving hydrogen on the surface of gold nanoparticles.

The Synthesis, Bonding, and Transformation of a Ligand‐Protected Gold Nanohydride Cluster

AbstractGold does not react with H2to form bulk hydrides. Here we report the synthesis and characterization of a gold nanohydride protected by diphosphine ligands, [Au22H4(dppo)6]2+[dppo=1,8‐bis(diphenylphosphino)octane]. The Au22core consists of two Au11units bonded by eight Au atoms not coordinated by the diphosphine ligands. The four H atoms are found to bridge the eight uncoordinated Au atoms at the interface. Each Au11unit can be viewed as a tetravalent superatom forming four delocalized Au‐H‐Au bonds, similar to the quadruple bond first discovered in the [Re2Cl8]2−inorganic cluster. The [Au22H4(dppo)6]2+nanohydride is found to lose H atoms over an extended time via H evolution (H2), proton (H+) and hydride (H−) releases. This complete repertoire of H‐related transformations suggests that the [Au22H4(dppo)6]2+nanohydride is a versatile model catalyst for understanding the mechanisms of chemical reactions involving hydrogen on the surface of gold nanoparticles.

Phenylchromium(III) Chemistry Revisited 100 Years after Franz Hein (Part II): From LinCrPh3+n(thf)x (n = 1, 2, 3) to Dimeric Triphenylchromate(II) Complexes

Polyphenylchromium(III) organometallics with various phenylation degrees and stabilized by diverse Lewis bases with various donor strengths and denticity were investigated in order to better understand the formation of (η6-arene)chromium complexes according to the procedure of Franz Hein (1892–1976) [ Organometallics 2019, 38, 498−511, DOI: 10.1021/acs.organomet.8b00811]. Part II focuses on hexa-, penta-, and tetraphenylchromates(III). Chromium(III) compounds with a lower phenylation degree will be discussed in a future part III. The numbering scheme of the complexes relates to the number of Cr-bound phenyl substituents. Hexaphenylchromate(III): The reaction of Ph3Cr(thf)3·0.25dx (3) (dx = 1,4-dioxane) with an ethereal solution of phenyllithium yields yellow-orange [Li3CrPh6(thf)2.3(OEt2)0.7] (6-thf-OEt2) which slowly degrades in contact with the reaction solution leading to emerald-green crystals of [{(Et2O)Li}2Ph3Cr(μ-O)]2 (3-Li2O). Pentaphenylchromate(III): Compound 6-thf-OEt2 reacts with 1 equiv of HCl–OEt2 solution to turquoise [{(thf)2Li}{(Et2O)Li}CrPh5] (5-thf-OEt2) that reacts with THF to the green contact ion pair [{(thf)2Li}2CrPh5] (5-thf) and with 12-crown-4 (12C4) to the light green solvent-separated ion pair [(12C4)Li(thf)]2 [CrPh5] (5-thf-12C4). Refluxing of 5-thf-OEt2 in diethyl ether leads to ether degradation and formation of 3-Li2O, whereas 5-thf-12C4 liberates biphenyl under similar reaction conditions. Tetraphenylchromate(III): The reaction of 3 with 1 equiv of phenyllithium in THF leads to a green reaction mixture. At −50 °C, red [(thf)4Li] [cis-(thf)2CrPh4]·2THF (4-thf) crystallizes which reversibly transforms into a green oil above −50 °C. Upon acidolysis of 5-thf-OEt2 with 1 equiv of HCl–OEt2 at −20 °C, the intermediately formed red complex is reduced to the dinuclear chromate(II) [{(thf)Li}CrPh3]2 (3-CrII-thf) (Cr–Cr 187.66(8) pm). Recrystallization of this product from THF yields solvent-separated [(thf)4Li]2 [(CrPh3)2] (3-CrII-thf4) with a Cr–Cr quadruple bond (Cr–Cr 183.7(2) pm) without contacts between the lithium ions and Cr-bound phenyl groups. Complex 3-CrII-thf reacts at room temperature in diethyl ether to the sandwich complexes bis(biphenyl)chromium(0) [(η6-Ph2)2Cr0] (π-4) and benzene-biphenylchromium(0) [(η6-C6H6)(η6-Ph2)Cr0] (π-3). Compounds in bold letters are authenticated by X-ray structure determinations.

Arm-length-dependent phase transformation and dual dynamic healing behavior of supramolecular networks consisting of ureidopyrimidinone-end-functionalized semi-crystalline star polymers

A rigid crystalline structure suppresses chain mobility and diffusion of self-healing supramolecular networks, lowering their healing capabilities. Herein it is presented that the incorporation of crystals in self-healing supramolecular networks as an effective way to overcome the inherent lack of mechanical strength of self-healing supramolecular networks, instead of a healing barrier. We prepare dual dynamic supramolecular networks composed of two types of dynamic physical bonds, i.e., quadruple hydrogen bonds and crystalline physical bonds, using the ureidopyrimidinone (UPy)-end-functionalized semi-crystalline star-shaped poly(ε-caprolactone)s (USPs). With increasing arm-length of the USPs, the phase of the network changes from UPy-stacked crystals to an amorphous phase and further to chain-folding polymeric crystals. The healing capabilities are also enhanced with increasing the arm-length of the USPs. Such changes in phase and healing capability are strongly associated with the crosslinking density of the network. In addition, the appropriate arm-length balance of USPs can provide a mechanically rigid semi-crystalline supramolecular network with a highly efficient healing property due to their reversible dual dynamic features, associated with the re-association of UPy quadruple hydrogen bonds and restoration of crystalline physical bonds during healing.

Tough and Multi-Recyclable Cross-Linked Supramolecular Polyureas via Incorporating Noncovalent Bonds into Main-Chains.

Covalent thermosets generally exhibit robust mechanical properties, while they are fragile and lack the ability to be reprocessed or recycled. Herein, a new strategy of incorporating noncovalent bonds into main-chains is developed to construct tough and multi-recyclable cross-linked supramolecular polyureas (CSPU), which are prepared via the copolymerization of diisocyanate monomers, noncovalently bonded diamine monomers linked by quadruple hydrogen bonds, and covalent diamine/triamine monomers. The CSPU exhibit remarkable solvent resistance and outstanding mechanical properties owing to the covalent cross-linking via triamine monomer. Through the incorporation of 9.7% and 14.6% quadruple hydrogen bonded diamine monomer, the transparent CSPU films are endowed with superior toughness of 74.17 and 124.17 MJm-3 , respectively. Impressively, even after five generations of recycling processes, the mechanical properties of reprocessed CSPU can recover more than 95% of their original properties, displaying excellent multiple recyclablity. As a result, the superior toughness, remarkable solvent resistance, high transparency, and excellent multiple recyclability are well-combined in the CSPU. It is highly anticipated that this line of research will provide a facile and general method to construct various cross-linked polymer materials with superior recyclability and mechanical properties.

Quadruple Bonding in the Ground and Low-Lying Excited States of the Diatomic Molecules TcN, RuC, RhB, and PdBe.

Multiple bonds between atoms are one of the most fundamental aspects of chemistry. Double and triple bonds are quite common, while quadruple bonds are a true oddity and very rare for the main group elements. Identifying molecules containing quadruple bonds is very important and, even more so, determining the necessary requirements for the existence of such bonds. Here we present high-level theoretical calculations on the isoelectronic MX molecules, i.e., TcN, RuC, RhB, and PdBe, showing that such a quadruple bond with main group elements is not that uncommon. We found that quadruple bonds are formed in their ground states X3Δ (TcN) and Χ1Σ+ (RuC, RhB, and PdBe) and in the two lowest excited states of TcN (1Σ+, 1Δ), RuC (1,3Δ), and RhB (1,3Δ). The quadruple bonds consist of two π and two σ bonds: (4dxz-2px)2, (4dyz-2py)2, (4dz2-2pz)2, and 5s0 ← 2s2 (1Σ+) or 5pz0←2s2 (1,3Δ). Bond lengths, dissociation energies, dipole moments, spectroscopic parameters, and relative energy ordering of the states were calculated via multireference and coupled cluster methodology using the aug-cc-pV5ZX(-PP)M basis sets. We study how the atomic states involved and how the gradual transition from covalent to dative bond, from TcN to PdBe, influence all of the calculated data, such as bond dissociation energies, bond lengths, and relative energy ordering of the states. Finally, we report the requirements for the occurrence of such bonds in molecular systems. All Be, B, C, and N atoms combining with the appropriate second-row transition metal can form quadruple bonds, while they cannot form such bonds with the first-row transition metals.

Shape Memory and Self-Healing Nanocomposites with POSS–POSS Interactions and Quadruple Hydrogen Bonds

The organic–inorganic nanocomposites were constructed via polyhedral oligomeric silsesquioxanes (POSS)–POSS interactions and supramolecular quadruple hydrogen bonds. First, a double-decker silsesqu...

Encapsulation of Dirhenium(III) Carboxylates into Zirconium Phosphate

Present work reports the synthesis of zirconium phosphate nanoparticles containing dirhenium(III) substance bis-dimethylsulfoxide-cis-tetrachlorodi-?-pivalatodirhenium(III) with formula cis-Re2(C(CH3)3COO)2Cl4?2DMSO (I) and q-zirconium phosphate with formula q-Zr(HPO4)2?6H2O (ZrP). The intercalation process was monitored by EAS. Due to the spectral characteristics of the quadruple bond the conclusion was made that the obtained intercalated compounds had cis-configuration of ligands around cluster dirhenium fragment. The proposed mechanism of intercalation includes the substitution of the axial ligands of I by phosphate groups of ZrP first on the surface of ZrP, than in the inner layers. Two received products of the intercalation were characterized by SEM, XRPD, FT-IR, TGA analysis witnessing about successful intercalation process. The formation of new phases with interlayer distances of 10.53 - 16.6 ? was found, the average size of obtained platelets was 100-200 nm.

Self‐healing supramolecular waterborne polyurethane dispersions with quadruple hydrogen bonds in main chain

AbstractA facile method for preparing supramolecular waterborne polyurethane (WPU) based on quadruple hydrogen bonds (4H‐WPU) is reported. Herein, 4H‐WPU with quadruple hydrogen bonds in main chain were synthesized by poly (1,4‐buthylene‐neopentylene adipate glycol) as soft segment, 2‐ureido‐4[1H]‐pyrimidinone (UPy) functionalized monomer, isophorone diisocyanate, 2,2‐Bis(hydroxymethyl)propionic acid (hydrophilic monomer), isophorondiamine, triethylamine (neutralizer), and monoethanolamine (blocking agent) as hard segment. The molecular weight of 4H‐WPU was controlled around 18,000 consistently. The properties of 4H‐WPU with different content of hydrophilic group, hard segment, and UPy units were characterized and the results could provide the reference for preparing supramolecular WPU with high mechanical and self‐healing performance while maintaining dispersion stability. The tensile strength of 4H‐WPU was 10 times of the blank sample. The healing time of scratched 4H‐WPU film was inversely proportional to the content of UPy‐ functionalized monomer and the shortest healing time is 2.5 hr at 80°C. Mechanical performance of healed films can be restored to more than 90%.