Network Of Intermolecular Hydrogen Bonds Research Articles

Different States of water in α-Cyclodextrin hydrates

The pressure of saturated and unsaturated water vapor over α-CD·nH2O hydrates has been measured by static method with membrane-gauge manometer under conditions of complete loss of water. The temperature dependences of water vapor pressure have been obtained in the wide range of temperatures (287–469 K), pressures (0.04–34.95 kPa) and water content (0.17 ≤ n ≤ 6.0).The data obtained indicate the presence of water molecules with different volatility in α-CD·nH2O hydrates. Water molecules with lower volatility can be considered “external”, included in the network of intermolecular hydrogen bonds, while water molecules with higher volatility, discovered in our previous study, are considered “internal”, presumably located in the α-CD cavity. For each composition, the amount of “external” and “internal” water has been determined and the equations described the dependence of the content of each type of water on n in α-CD·nH2O have been obtained. The analytical expressions for the lnp – 1/T dependences as well as the values of enthalpy and entropy of processes studied have been calculated. Experimental data were used to obtain the Gibbs energy changes when “external” water molecules bind to the α-CD framework. The values obtained are differed from the values for “internal” water given in our previous study. The phase transition in α-CD·nH2O revealed in our previous study is also observed in this work and its thermodynamic characteristics are in good agreement with the results obtained earlier. The findings have been confirmed by 1H NMR studies.

A High-capacity Benzoquinone Derivative Anode for All-organic Long-cycle Aqueous Proton Batteries.

Quinone compounds, with the ability to uptake protons, are promising electrodes for aqueous batteries. However, their application is limited by the mediocre working potential range and inferior rate performance. Herein, we examined quinones bearing different substituents, and for the first time introduce tetraamino-1,4-benzoquinone (TABQ) as anode material for proton batteries. The strong electron-donating amino groups can effectively narrow the band gap and negatively shift the redox potentials of quinone material. The protonation of amino groups and the amorphization of structure result in the formation of an intermolecular hydrogen-bond network, supporting Grotthuss-type proton conduction in the electrode with a low activation energy of 192.7 meV. The energy storage mechanism revealed by operando FT-IR and ex-situ XPS features a reversible quinone-hydroquinone conversion during cycling. TABQ demonstrates a remarkable specific capacity of 307 mAh g-1 at 1 A g-1, which is the highest among organic proton electrodes. An all-organic proton battery of TABQ//TCBQ has also been developed, achieving exceptional stability of 3500 cycles at room temperature and excellent performance at sub-zero temperatures.

A Molten Alkali Approach to Tailor Hydroxyl Groups of Hexaazatrinaphthalene Toward High-Capacity and Low-Potential Anode of Aqueous Proton Batteries.

Hexaazatrinaphthalene (HATN) has attracted a lot of attention in aqueous proton batteries (APBs). However, its redox potential as an anode is insufficiently negative. The introduction of electron-donating substituent groups, such as hydroxyl groups, is considered as a good approach to reduce the redox potential of HATN. Nevertheless, manufacturing hydroxyl-substituted HATN (HATN-OH) requires either expensive precursors or multi-step process, limiting their research. Herein, a straightforward strategy is proposed to synthesize HATN-OH based on the nucleophilic substitution reaction of halogenated HATN in a molten alkali. The redox potential of 1,2,7,8,13,14-hexahydroxy-5,6,11,12,17,18-hexaazatrinaphthalene (34-HATN-6OH) electrode may be lowered by 0.15V in comparison to HATN, and exhibits a high specific capacity, low redox potential, remarkable rate capability, and outstanding long-term cycling performance. The electrochemical redox kinetics is significantly enhanced owing to the formation of rapid proton transport channels created by intermolecular hydrogen bond network. The assembled MnO2||34-HATN-6OH full battery delivers a high discharge voltage (1.16V) and cycling stability (74% capacity retention after 5000 cycles). This study provides a general cost-effective molten alkali approach for the synthesis of hydroxyl-substituted conjugated small molecules from their halogenated counterparts and further enriches the regulation means of electro-chemical performances of organic electrodes for enabling high-capacity and high-voltage APBs.

Effect of ionic bonding on luminescence properties of histidine maleic anhydride derivatives

Polymeric materials exhibiting room-temperature phosphorescent (RTP) have attracted wide attention for their easy synthesis, low toxicity, and applications in various fields such as data encryption, cell imaging, information security and other fields. Nevertheless, the conventional ways of preparing such materials are mainly focused on doping, which may suffer from phase separation, poor compatibility, and lack of effective methods to promote intersystem crossing and suppress the nonradiative deactivation rates. Herein, a series of polymers with fluorescence and phosphorescence dual emission were prepared by simple radical solution copolymerization. Through rigid ion-bonded cross-linked networks and cross-linked hydrogen-bonded networks between the polymer chains, the non-radiative jumps and achieve ultra-long phosphorescence lifetimes were able to suppress. By suppressing non-radiative transitions through rigid ion-bonded cross-linked networks and intermolecular hydrogen-bonding networks between polymer chains, ultra-long phosphorescence is achieved. Impressively, a LRTP lifetime of up to 815.38 ms in polymers under ambientconditions is set up. Moreover, in this study, phosphorescence emission can be easily tuned by balancing ion radius and charge states. These results outline the construction of polymeric materials, endowing traditional polymers with new characteristics and promising potential applications.

Di-μ-adipato-κ4 O 1,O 1':O 6,O 6'-bis-[(2,2'-di-pyridyl-amine-κ2 N,N')zinc(II)] trihydrate.

The title compound, [Zn2(C6H8O4)2(C10H9N3)2]·3H2O or {Zn2[(C5H4N)2NH]2[μ-(CH2)4(COO)2]2}·3H2O, was separ-ated from the solvothermal reaction of zinc(II) sulfate hepta-hydrate, 2,2'-di-pyridyl-amine and sodium adipate. The dinuclear metal complex has a centrosymmetric structure, with the ZnII atom adopting a highly distorted octa-hedral coordination sphere composed of four oxygen atoms from bridging adipato ligands and two pyridine nitro-gen atoms. In the crystal, the title compound aggregates into a tri-periodic supra-molecular structure through inter-molecular hydrogen-bonding networks of the form O-H⋯O and N-H⋯O.

High-Performance Azo Cathodes Enabled by N-Heteroatomic Substitution for Zinc Batteries with a Self-Charging Capability.

Redox-active azo compounds are emerging as promising cathode materials due to their multi-electron redox capacity and fast redox response. However, their practical application is often limited by low output voltage and poor thermal stability. Herein, we use a heteroatomic substitution strategy to develop 4,4'-azopyridine. This modification results in a 350 mV increase in reduction potential compared to traditional azobenzene, increasing the energy density at the material level from 187 to 291 Wh kg-1. The introduced heteroatoms not only raise the melting point of azo compounds from 68 °C to 112 °C by forming an intermolecular hydrogen-bond network but also improves electrode kinetics by reducing energy band gaps. Moreover, 4,4'-azopyridine forms metal-ligand complexes with Zn2+ ions, which further self-assemble into a robust superstructure, acting as a molecular conductor to facilitate charge transfer. Consequently, the batteries display a good rate performance (192 mAh g-1 at 20 C) and an ultra-long lifespan of 60,000 cycles. Notably, we disclose that the depleted batteries spontaneously self-charge when exposed to air, marking a significant advancement in the development of self-powered aqueous systems.

A Nickel-Based Semiconductor Hybrid Material with Significant Dielectric Constant for Electronic Capacitors.

A novel semiconducting Ni(II)-based hybrid material with the formula (C7H12N2) NiCl4, which exhibits interesting optical and electrical properties, is reported. The crystal structure was investigated using SCXRD, whereas physical properties were studied by means of thermal analysis, Ft-Infrared, optical, and electrical measurements. Its crystal packing is formed through organic rings surrounded by inorganic [NiCl4]2- tetrahedral and stacked along the a-crystallographic axis. This arrangement is stabilized by a dense network of intermolecular hydrogen bonds. The investigated compound displayed a wide absorption range across the visible spectrum, characterized by an optical gap energy of 2.64 eV, indicating its semiconducting nature and efficient sunlight absorption capabilities across various wavelengths. Such features are of utmost importance in achieving a high energy conversion efficiency in solar cell applications. Further analyses of the thermal behavior using differential scanning calorimetry revealed a single-phase transition occurring at around 413 K, which was further confirmed through electrical measurements. A deep investigation of the electric and dielectric performances demonstrated a significant dielectric constant (ε' ∼ 104) at low frequencies and low dielectric loss at high frequencies. Thus, it highlights its exceptional dielectric potential, particularly in applications related to electronic capacitors.

The Synergistic Influence of the Hydrophobic and Hydrophilic Ends on the Primary Dielectric Relaxation Rate of Methanol

The primary dielectric relaxation process of monoalcohols typically exhibits characteristic Debye behavior, and the factors influencing its rate have become a research focus in recent years. It is generally believed that the hydrophilic end (i.e., the hydroxyl group) of alcohol molecules plays a major role in the primary dielectric relaxation process through hydrogen bonding networks, while the hydrophobic end mainly exerts an indirect effect by influencing the formation of intermolecular hydrogen bonds. This study systematically investigates the factors influencing the primary dielectric relaxation process of methanol using molecular dynamics simulations. As the simplest alcohol molecule, studying methanol can provide insights into the common characteristics of monohydroxy alcohols and even alcohols in general. The well-known "wait-and-switch" model currently emphasizes the impact of hydrogen bond partner concentration on the primary dielectric relaxation rate of the system. In this study, we systematically investigated the factors influencing the primary dielectric relaxation rate of methanol by independently adjusting the O-H bond length (<i>d<sub>oh</sub></i>), the C-O bond length (<i>d<sub>oc</sub></i>), and the methyl diameter (<i>σ<sub>methyl</sub></i>) of methanol molecules, and provided significant extensions to the "wait-and-switch" model:1) By adjusting <i>doh</i>, we found that a stronger total hydrogen bond energy (<i>U<sub>HB</sub></i>) in the system enhances the correlation of molecular motion, slowing down the reorientation rate of molecules and, consequently, the primary dielectric relaxation process of the system. 2) By adjusting <i>d<sub>co</sub></i>, we discovered that a longer hydrophobic end not only slows down the primary dielectric relaxation process by stabilizing the intermolecular hydrogen bond network but also directly reduces the rate of this process. 3) By adjusting <i>σ<sub>methyl</sub></i>, we found that an excessively small <i>σ<sub>methyl</sub></i> is detrimental to the stability of the hydrogen bond network, while an excessively large <i>σ<sub>methyl</sub></i> hinders the formation of hydrogen bonds. Both cases negatively affect the correlation of molecular motion. The primary dielectric relaxation process of the system is slowest when <i>σ<sub>methyl</sub></i> is at a moderate level. It was ultimately found that factors such as <i>U<sub>HB</sub></i> and the volume of the correlated motion (<i>V<sub>CM</sub></i>), along with the concentration of hydrogen bond partners in the system, collectively form the key elements influencing the primary dielectric relaxation rate of the system. Our results can reasonably explain experimental phenomena that the original "wait-and-switch" model could not account for. This study contributes to a deeper understanding of the relaxation processes of alcohol molecules and their physical origins.

Proton exchange of carbonic acid and methylamine complex accelerated by a single-water molecule via intermolecular hydrogen bonding: A theoretical investigation

A theoretical investigation of the microsolvation effect on proton exchange (PE) between carbonic acid and methylamine (CA-MTA) has been explored by quantum dynamics simulations. The structural, energy, and dynamic properties of the CA-MTA complex with and without an explicit water molecule are elucidated at the molecular level. The reactions from this study have been clarified into different types: single-step PE (SSPE) and stepwise PE (SWPE). Without the water molecule, the SSPE mechanism is hardly found but observable with a low probability of 0.2. In particular, the water molecule interacting through intermolecular hydrogen-bonded network between CA and MTA in CA-MTA-Win could affect PE by showing both SSPE and SWPE mechanisms. In addition, the existing water molecule plays the significant role in shortening intermolecular hydrogen bonding interactions within the complex resulting in increasing the probability of PE up to 0.92 especially in CA-MTA-Wout. Hence, one water molecule could be used to provide reliable results to represent the significant activity that occurs for the proton exchangeability of the CA and MTA complex.

Process intensification in the ketalization of glycerol with acetone catalyzed by NaHSO4-NaOH catalytic system

Glycerol is one cheap byproduct in production of biodiesel, and the ketalization of glycerol is one of the most important and effective way to increase its value and improve the sustainability of biodiesel. The ketalization of glycerol with acetone is always catalyzed by acid catalyst. In this work, NaOH was added into the reaction system during the ketalization process catalyzed by NaHSO4, and it was found for the first time that this process could be intensified by NaOH significantly. The acidity of acidic catalysts would affect their catalytic performance. Increasing reaction temperature and time, molar ratio of acetone to glycerol, the dosage of NaHSO4 and molar ratio of NaOH to NaHSO4 could favor for the ketalization, but the excessive formation of water and the evaporation of acetone would retard the reaction. The addition of NaOH could destroy the intermolecular hydrogen bond network of glycerol molecules, making the hydroxyl groups bared in free state, and increase the amount of electrophilic transition state of acetone, which help to promote the transformation of glycerol to solketal significantly. With the assistance of NaOH, the conversion rate of glycerol could even reach 97.58 % without extracting water continuously from the reaction system.

Explorations on the synthesis, structure, DFT, DNA binding properties and molecular docking of tridentate Schiff base Copper (II) complexes

Copper(II) Schiff base complexes of (2-Hydroxy-benzaldehyde)-amino acid have been synthesized and characterized. The complexes' single-crystal X-ray structures were studied, and it was discovered that the 4,4-bipyridine functions as a bidentate bridging ligand connecting two Cu(II) ions. In order to assemble the complicated components into a three-dimensional chain structure and arrange the 4,4-bipyridine molecules into parallel sheets, intermolecular hydrogen bonds are essential. A robust intermolecular hydrogen bond network including water oxygen atoms strengthens the connection between water molecules and phenolate oxygen atoms from the ligand, which is produced from salicylaldehyde. The complexes' interaction with DNA was investigated by UV–Visible, fluorescence and CD spectrophotometric methods, which indicate that the complexes favourably bind to the groove in the DNA. The DNA binding affinity was confirmed by molecular docking. Additionally, DFT calculations were used to determine the stable geometry for these complexes. A thorough understanding of the interactions of these synthesized complexes was achieved through an intensive molecular docking research. These findings show that the complexes have a high affinity for DNA binding and considerable groove binding. Notably, Complex 1 showed a greater affinity for DNA than Complex 2.

Efficient production of chito-oligosaccharides through microwave-assisted hydrothermal and low-acid-mediated degradation and deacetylation of chitin

The conventional method for producing chitin oligosaccharides involves high-temperature hydrolysis in high-concentration acid. In this study, we present an alternative method using microwave-assisted hydrothermal and diluted acid (0.12 mol/L) hydrolysis. After batched reactions, the liquefaction rate of chitin can reach almost 50%, and the sugar product yield is about 27%. Furthermore, this method leads to the reduction of the average particle size of chitin by approximately 70%, a decrease in the degree of acetylation by about 35%, partial destruction of the intermolecular hydrogen bond network, and the breaking of glycosidic bonds. These changes result in the exposure of more hydroxyl groups and enzyme binding sites, which may facilitate a subsequent enzymatic treatment. The method is a feasible alternative to obtain chitin oligosaccharides with a low environmental impact and operating cost.

Breaking Consecutive Hydrogen‐Bond Network Toward High‐Rate Hydrous Organic Zinc Batteries

AbstractZinc batteries hold great potential for stationary energy storage but suffer from severe dendrite growth, corrosion, and hydrogen evolution troubles in aqueous electrolytes. Despite the impressive efficacy of non‐flammable hydrous organic electrolytes in addressing these problems, the insufficient ionic conductivity hinders the rate capability and practicability of hydrous organic Zn batteries. Here, methanol is proposed as a co‐solvent for ethylene glycol (EG)‐based hydrous organic electrolytes, where its methyl terminal group can interrupt the continuous intermolecular hydrogen bond network among EG. The new hydrous organic electrolyte exhibits a doubled ionic conductivity without sacrificing the exceptional nonflammability. As a result, the Zn anode exhibits a long‐term cycling stability over 4000 h at 0.5 mA cm−2, a high Coulombic efficiency of 99.5%, high‐rate capability up to 20 mA cm‒2, and impressive low‐temperature tolerance of ‒60 °C. The Zn||V2O5 pouch cell with the electrolyte is capable of operating under extreme operation conditions involving needling, package breakage, and even exposure to fire. This work paves an avenue toward electrolyte design for high‐rate practical Zn batteries and beyond.

Aqua-{μ-1,4-bis-[(1,4,7,10-tetra-aza-cyclo-dodecan-1-yl)meth-yl]benzene}(nitrato-κO)dicopper(II) tris-(nitrate) trihydrate.

In the title dinuclear CuII complex, [Cu2(NO3)(C24H46N8)(H2O)](NO3)3·3H2O, the two CuII mol-ecules both have a square-pyramidal geometry, but the ligands in the axial positions are different: a water mol-ecule and a nitrate ion. All nitrate ions, water mol-ecules, and N-H groups are involved in an inter-molecular hydrogen-bond network.

Characterizing the thermal phase behaviour of fipronil polymorphs

This manuscript reports the investigation of the polymorphic behaviour of fipronil using a systematic comparison of the thermochemical and structural properties of different crystal forms obtained in this study as well as those previously reported in literature. The analytical techniques employed include DSC, TGA, PXRD, SCXRD and hot stage microscopy. DSC proved particularly useful because it made it possible to differentiate between the two different crystal forms found in the as-received neat fipronil. The DSC scans revealed the presence of two polymorphs which had melting endotherms with peak maxima at ca. 196 °C and 205 °C, respectively. These polymorphs were successfully separated via sublimation and resulted in a metastable, lower melting polymorph in the sublimate and a thermodynamically stable, higher melting form in the sublimation residue. Clear evidence for the instability of the lower melting polymorph was found when the endotherms were examined under a range of heating rates. The proportion of the metastable form appeared to increase as the rate was increased, indicating that the metastable form underwent a solid–solid phase transition to the stable form at low heating rates. Recrystallization of fipronil from different solvents yielded five different forms. TGA curves revealed that all forms, except the acetone-derived one, were solvate pseudo-polymorphs that showed solvent loss between 60 and 100 °C. The acetone-derived sample was a hemihydrate that only started to show mass loss at 120 °C. SCXRD studies revealed that three of the five forms have similar structural characteristics, while the other two forms differ notably from each other and the rest of the structures. Despite these structural differences, all five forms exhibit near-identical intra- and intermolecular hydrogen bond networks.

Extreme UV Resist Exhibiting Synergism between Chemical and Physical Crosslinking Mechanisms.

Carbon-fluorine bonds in fluorinated molecules can undergo homolytic cleavage reactions when electrons are injected, and the resulting radicals combine to form network structures characterized by reduced solubility. This crosslinking chemistry suggests a new category of patterning materials that function under electron beam (e-beam) and extreme ultraviolet (EUV) lithographic conditions. Although this chemistry enables the production of 50 nm or smaller-sized features of simple fluoroalkylated polymers, it is limited by the need for relatively large amounts of irradiation energy to achieve required solubility changes. Therefore, this study was undertaken to devise a sensitivity-enhancing strategy based on a synergistic combination of radical crosslinking and hydrogen-bonding interactions between highly fluoroalkylated copolymers. An alternating copolymer was synthesized using tert-butoxystyrene and a fluoroalkylated maleimide, the former of which produces active hydrogens through catalytic acidolysis reactions. When the polymer was blended with a catalytic amount of a photoacid generator and subjected to lithographic patterning tests under e-beam and EUV irradiation, the deprotection reactions of tert-butoxy moieties proceeded at room temperature and led to a solubility decrease. We presume the small number of hydroxyl moieties produced formed an intermolecular hydrogen-bonding network, which acted synergistically with the covalent crosslinks generated by C-F bonds. When 30 nm features of copolymer thin films were fabricated by EUV lithography, sensitivity was improved by 25-34% without significant deterioration of pattern quality, especially line-edge roughness. These results demonstrate that EUV resists with improved patterning capabilities can be achieved by combining catalytic acidolysis reactions and noncatalytic crosslinking chemistry.

Natural crystalline fibers of (E)-(R)-4-thujanol: green kilogram production from a selected wild thyme. X-ray and NMR characterization of a spiral structure

(E)-(R)-4-Thujanol present in thyme essential oils is an important aromatic ingredient for food, cosmetic and pharmaceutical applications. Until now, its extraction was challenging due to its low content in classical aromatic plants such as thyme or marjoram. Although this molecule is synthetically available, there is no production on an industrial scale because of very time-consuming and expensive chemical processes. We report here for the first time a new eco-responsible method to produce (E)-(R)-4-thujanol crystals on a kilogram scale. This new milestone is based on 2 fundamental research gaps: i) the selection of a wild thyme (Thymus vulgaris) for its high content of (E)-(R)-4-thujanol and its careful harvesting in the hills of French Provence and ii) a steam distillation producing an organic aromatic oil which aggregates spontaneously due to a favorable amphipathic partition at the air-water interface. Gas chromatography revealed a composition made of (E)-(R)-4-thujanol (76%), thymol (5%), β-myrcene (2,8%) and other minor monoterpenes. The white aggregate submitted to a cycle of sublimation/crystallization, led to accumulating translucent fibers made of (E)-(R)-4-thujanol (98%). X-ray diffraction unambiguously demonstrated that crystals of (E)-(R)-4-thujanol form a trimer (monoclinic asymmetric (C2)) unit composed of three independent (E)-(R)-4-thujanol molecules. The trimer is further organized into a chiral P-type supramolecular helix of trimers through a network of intermolecular hydrogen bonds. This study is based on the cheap, easy and eco-responsible kilogram production of (E)-(R)-4-thujanol crystals may open up new opportunities for the flavor, fragrance and pharmaceutical industries. Fibers of (E)-(R)-4-thujanol may also have applications as bio-active fibrous assemblies.

A disposable paper-based microfluidic electrochemical cell equipped with graphite-supported gold nanoparticles modified electrode for gallic acid determination

The combination of µPAD with electrochemical transducers has gained advantages of miniaturization, high sensitivity, selectivity, simplicity of instrumentation, portability, rapid analysis, and so on. In this work, the development of a 3D paper-based microfluidic electrochemical device (3D-ePAD) for the determination of gallic acid (GA) was presented. The 3D-ePAD is composed of three electrodes (working, reference, and counter electrodes) in which the hydrophilic area of the working electrode was manually screen-printed and modified with graphite-supported AuNPs(AuNPs/C) ink. The evaluation of the electrochemical oxidation process of GA at modified and unmodified electrodes at 3D-ePAD indicated the improvement of anodic current responses at the AuNPs/C modified electrode which can be attributed to the intermolecular hydrogen-bonded network between AuNPs and GA. For quantitative determination of GA, the amperometric experiments were investigated under optimal conditions in which a linear relationship between the GA concentration and the recorded current was achieved. The sensor displays a good linear range of 1.0 to 100.0 μM and 0.1 to 2.0 mM for GA determination. The limit of detection (LOD) of 0.89 μM was achieved for GA by 3D-ePAD. Conclusively, the 3D-ePAD was performed successfully for the determination of GA in tea samples.

Antioxidant and Biocompatible CO2‐Based Biocomposites from Vegetable Wastes for Active Food Packaging

AbstractIn this study, an innovative and scalable strategy is developed to valorize vegetable wastes as valuable and cost‐effective natural antioxidant resources in the development of CO2‐based biocomposites. The dried vegetable stems (parsley and spinach) are firstly micronized and then incorporated into a CO2‐derived poly(propylene carbonate) (PPC) polymer matrix by hot compression molding technique. The vegetable waste microparticles are found to be homogenously dispersed within the PPC matrix. Due to the establishment of a strong intermolecular hydrogen bond network between PPC and vegetable waste microparticles, the obtained biocomposites exhibit improved mechanical properties compared to pure PPC, comparable to these of common plastics use for packaging materials. The water barrier properties of the developed biocomposites are also promising for packaging applications. Additionally, the developed biocomposites are found to be biocompatible and show effective antioxidant scavenging activity against 2,2′‐azinobis(3‐ethylbenzothiazoline‐6‐sulfonic acid) radical cation (ABTS•+). Therefore, these antioxidant and biocompatible biocomposites deriving from CO2 greenhouse gas and industrial agro‐food wastes are of great interest for active food packaging applications.

Supramolecular Helical Assemblies of Dirhodium(II) Paddlewheels with 1,4-Diazabicyclo[2.2.2]octane: A Remarkable Substituent Effect on the Helical Sense Preference and Amplification of the Helical Handedness Excess of Metallo-Supramolecular Helical Polymers.

We report unique coordination-driven supramolecular helical assemblies of a series of dirhodium(II) tetracarboxylate paddlewheels bearing chiral phenyl- or methyl-substituted amide-bound m-terphenyl residues with triethylene glycol monomethyl ether (TEG) or n-dodecyl tails through a 1:1 complexation with 1,4-diazabicyclo[2.2.2]octane (DABCO). The chiral dirhodium complexes with DABCO in CHCl3/n-hexane (1:1) form one-handed helical coordination polymers with a controlled propeller chirality at the m-terphenyl groups, which are stabilized by intermolecular hydrogen-bonding networks between the adjacent amide groups at the periphery mainly via a cooperative nucleation-elongation mechanism as supported by circular dichroism (CD), vibrational CD, and variable-temperature (VT) absorption and CD analyses. The VT visible-absorption titrations revealed the temperature-dependent changes in the degree of polymerization. The columnar supramolecular helical structures were elucidated by X-ray diffraction and atomic force microscopy. The helix sense of the homopolymer carrying the bulky phenyl and n-dodecyl substituents is opposite those of other chiral homopolymers despite having the same absolute configuration at the pendants. A remarkably strong "sergeants and soldiers" (S&S) effect was observed in most of the chiral/achiral copolymers, while the copolymers of the bulky chiral phenyl-substituted dirhodium complexes with n-dodecyl chains displayed an "abnormal" S&S effect accompanied by an inversion of the helix sense, which could be switched to a "normal" S&S effect by changing the solvent composition. A nonracemic dirhodium complex of 20% enantiomeric excess bearing the less bulky chiral methyl substituents with n-dodecyl chains assembled with DABCO to form an almost one-handed helix (the "majority rule" (MR) effect), whereas the three other nonracemic copolymers showed a weak MR effect.