Helicity Inversion Research Articles

Optical and Chiroptical Stimuli-Responsive Chiral AgNPs@H-Leu-Poly(phenylacetylene) Nanocomposites in Water.

Dynamic macroscopically chiral nanocomposites are prepared by combining silver nanoparticles (AgNPs) and dynamic helical poly(phenylacetylene)s (PPAs) bearing pendants functionalized with amino groups. These amino groups provide the nanocomposite with the ability to disperse in water along with high stability due to the interaction between the ammonium group and the AgNP. Moreover, the equilibrium between NH3+/NH2 produces a "blinking" contact between the PPA and the AgNPs, which allows total control of the dynamic helical behavior of the polymer. The use of acidic or neutral pH allows controlling the morphology of the nanocomposite, which consists of a nanosphere that has trapped inside it a single AgNP (pH = 2) or several AgNPs (pH = 7) with ca. 30 nm of diameter. These nanocomposites combine the optical and chiroptical stimuli-responsive properties of both components, AgNPs and PPAs. Thus, the controlled aggregation of the nanocomposite produced variations in the LSPR band of the AgNPs in a reversible manner. In turn, given that the chiral coating is selective to Ba2+, the presence of this metal ion caused a helical inversion of the chiral coating of the nanocomposite detected by electronic circular dichroism. Moreover, it is possible to distinguish between three metal ions in different oxidation states, such as Ce4+, Fe3+, and Hg2+, which produce different responses of the nanocomposite when oxidizing the AgNP to Ag+.

Redox-Triggered Reversible Switching between Dynamic and Quasi-static α-Helical Peptides.

We report the reversible transformation between a singly stapled dynamic α-helical peptide and a doubly stapled quasi-static one through redox-triggered dithiol/disulfide conversions of a stapling moiety. This process allows the rate of interconversion between the right-handed (P) and left-handed (M) α-helices to be altered by a factor of approximately 103 before and after the transformation. An as-obtained doubly stapled α-helical peptide, which is composed of an achiral peptide having an l-valine carboxylic acid residue at the C-terminus, a disulfide-based reversible staple, and a biphenyl-based fixed staple, adopts an (M)-rich form as a kinetically trapped state. The (M)-rich helix was subsequently transformed into the thermodynamically stable (P)-rich form in 1,1,2,2-tetrachloroethane with the half-life time (t1/2) of approximately 44 days at 25 °C. Reduction of the doubly stapled peptide with tri-n-butylphosphine in tetrahydrofuran/water (10/1, v/v) produced the corresponding singly stapled dynamic α-helical peptide bearing two thiol groups at the side chains, which underwent solvent-induced reversible helicity inversion. The resulting dithiol of the singly stapled peptide could be reoxidized to form the original doubly stapled form using 4,4'-dithiodipyridine. Furthermore, the P/M interconversion of a doubly stapled peptide with two flexible hydrocarbon-based staples is considerably more rapid than that with more rigid staples.

Broadband and efficient terahertz helicity inversion by a reconfigurable reflective metasurface based on vanadium dioxide

We experimentally demonstrate the broadband and highly efficient inversion of the rotation direction of the terahertz circular polarization achieved by a dynamic metasurface with vanadium dioxide (VO2). This metasurface converts linear polarization into circular polarization. The rotational direction of the output circular polarization can be reversed based on the VO2 phase transition. The VO2 state can be dynamically switched by injecting direct current into an on-chip circuit. To improve the terahertz-wave utilization efficiency, the metasurface is operated at an incident angle of 45°, thereby eliminating the beam splitter typically used to separate the outgoing wave from the incident wave at normal incidence. To achieve broadband operation, we employ a dispersion-cancelation strategy that cancels the dispersive phase responses between orthogonal linear polarizations. This strategy was previously developed for static metasurfaces; we have applied it to the design of dynamic metasurfaces. At a center frequency of 0.99 THz, the experimental evaluation demonstrated helicity switching with conversion efficiencies of 92% and 87% for the insulating and metallic states of VO2, respectively. Dispersion cancelation is simultaneously achieved for the insulating and metallic states of VO2, resulting in a relative bandwidth of 0.26, which is 3.2 times broader than that of a previously developed efficient dynamic metasurface.

Unusually Short H⋅⋅⋅H Contacts in Intramolecularly Cyclized Helically Fused Anthracenes.

The intramolecular coupling of dichloro-substituted helically fused anthracenes using the Yamamoto coupling yielded cyclized products with sterically congested molecular structures. The X-ray analysis and DFT calculations showed that the aromatic framework adopted a nonplanar structure with a twisted conformation about the newly formed single bond, which acts as a chiral axis. Interestingly, the X-ray structure obtained through the Hirshfeld atom refinement revealed short interatomic distances between the inner hydrogen atoms (1.648-1.692 Å), much shorter than the sum of their van der Waals radii. Owing to these unusually short contacts, the 1H NMR spectrum exhibited a significant deshielding (12.5 ppm) and a large nuclear Overhauser effect (44 %). Additionally, the IR spectrum displayed a high-frequency shift of the C-H stretching vibration. These observations, along with the noncovalent interaction plot indicative of a characteristic steric environment, strongly support the presence of steric hindrance. Moreover, dynamic NMR measurement of the mesityl-substituted derivative yielded a barrier to helical inversion of 84 kJ mol-1. The optical properties and crystal packing of the cyclized products are also reported.

Tailoring focal plane component intensities of polarization singular fields in a tight focusing system

The scientific community studies tight focusing of radially and azimuthally-polarized vector beams as it is a versatile solution for many applications. We offer a new method to produce tight focusing that ensures a more uniform intensity profile in multiple dimensions, providing a more versatile and stable solution. We manipulate the polarization of the radially and azimuthally polarized vector beams to find an optimal operating point. We examine in detail optical fields whose polarization states lie on the equator of the relevant Poincaré spheres namely, the fundamental Poincaré sphere, the hybrid order Poincaré sphere (HyOPS), and the higher order Poincaré sphere. We find via simulation that the fields falling on these equators have focal plane intensity distributions characterized by a single rotation parameter α\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\alpha$$\\end{document} determining the individual state of polarization. The strengths of the component field distributions vary with α\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\alpha$$\\end{document} and can be tuned to achieve equal strengths of longitudinal (z) and transverse (x and y) components at the focal plane. Without control of this parameter (e.g., using α=0\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\alpha =0$$\\end{document} in radially and α=π\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\alpha =\\pi$$\\end{document} in azimuthally-polarized vector beams) intensity in x and y components are at 20% of the z component. In our solution with α=π/2\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\alpha =\\pi /2$$\\end{document}, all components are at 80% of the maximum possible intensity of z. In examining the impact of α\\documentclass[12pt]{minimal} \\usepackage{amsmath} \\usepackage{wasysym} \\usepackage{amsfonts} \\usepackage{amssymb} \\usepackage{amsbsy} \\usepackage{mathrsfs} \\usepackage{upgreek} \\setlength{\\oddsidemargin}{-69pt} \\begin{document}$$\\alpha$$\\end{document} on a tightly focused beam, we also found that a helicity inversion of HyOPS beams causes a rotation of 180 degree in the axial intensity distribution.

Achiral Solvent Inversed Helical Pathway and Cosolvent Controlled Excited-State "Majority Rule" in Enantiomeric Dansulfonamide Assemblies.

Achiral solvents are commonly utilized to induce the self-assembly of chiral molecules. This study demonstrates that achiral solvents can trigger helicity inversion in the assemblies of dansyl amphiphiles and control the excited-state "majority rule" in assemblies composed of pure enantiomers, through variation of the cosolvent ratio. Specifically, enantiomers of dansyl amphiphiles self-assemble into helical structures with opposite handedness in methanol (MeOH) and acetonitrile (MeCN), together with inversed circular dichroism and circularly polarized luminescence (CPL) signals. When a mixture of MeOH and MeCN is employed, the achiral cosolvents collectively affect the CPL of the assemblies in a way similar to that of "mixed enantiomers". The dominant cosolvent governs the CPL signal. As the cosolvent composition shifts from pure MeCN to MeOH, the CPL signals undergo a significant inversion and amplification, with two maxima observed at ≈20% MeOH and 20% MeCN. This study deepens the comprehension of how achiral solvents modulate helical nanostructures and their excited-state chiroptical properties.

Structure and Chiroptical Properties of Anthra[1,2-a]anthracene-1-yl Dimers as New Biaryls.

Dimers of anthra[1,2-a]anthracene-1-yl units and its mesityl derivative were synthesized by Ni(0)-mediated coupling of the corresponding chloro derivatives as new biaryls. The X-ray analysis and DFT calculations revealed that two polycyclic aromatic units with nonplanar deformations took a twisted conformation about the single bond as a chiral axis. Enantiomers of the nonsubstituted compound were resolved by chiral HPLC, and the enantiopure samples showed intense Cotton effects at 321 nm in the circular dichroism (CD) spectra and emission bands at 449 nm in the circularly polarized luminescence (CPL) spectra with dissymmetry factor of |glum| 3.6×10-3. The absolute stereochemistry of this biaryl was determined by the theoretical calculation of CD spectrum by the time-dependent DFT method. The barrier to enantiomerization was determined to be 108 kJ mol-1 at 298 K. The dynamic process proceeded via a stepwise mechanism involving the helical inversion of each aromatic unit and the rotation about the biaryl axis as analyzed by the DFT calculations.

Revealing Pathway Complexity and Helical Inversion in Supramolecular Assemblies Through Solvent-Induced Radical Disparities.

New insights are raised to interpret pathway complexity in the supramolecular assembly of chiral triarylamine tris-amide (TATA) monomer. In cosolvent systems, the monomer undergoes entirely different assembly processes depending on the chemical feature of the two solvents. Specifically, 1,2-dichloroethane (DCE) and methylcyclohexane (MCH) cosolvent trigger the cooperative growth of monomers with M helical arrangement, and hierarchical thin nanobelts are further formed. But in DCE and hexane (HE) combination, a different pathway occurs where monomers go through isodesmic growth to generate twisted nanofibers with P helical arrangement. Moreover, the two distinct assemblies exhibit opposite excited-state chirality. The driving force for both assemblies is the formation of intermolecular hydrogen bonds between amide moieties. However, the mechanistic investigation indicates that radical and neutral triarylamine species go through distinct assembly phases by changing solvent structures. The neutralization of radicals in MCH plays a critical role in pathway complexity, which significantly impacts the overall supramolecular assembly process, giving rise to inversed supramolecular helicity and distinct morphologies. This differentiation in pathways affected by radicals provides a new approach to manipulate chiral supramolecular assembly process by facile solvent-solute interactions.

Properties of Antiferroelectric Mixtures Differing in the Amount of Added Racemate

Novel three-component liquid crystalline mixtures composed of chiral and achiral (racemic) liquid crystalline materials were designed and studied by polarizing optical microscopy, differential scanning calorimetry, and UV–VIS spectroscopy. The compositions of liquid crystalline mixtures were developed based on the composition of a two-component (binary) mixture marked as W-1000 with the following phase sequence: Cr ↔ SmCA* ↔ SmC* ↔ SmA* ↔ Iso. This mixture has an antiferroelectric (SmCA*) phase over a wide temperature range and exhibits a helical pitch inversion in this phase. All newly obtained mixtures occur in a wide temperature range of the SmCA* phase, while the ferroelectric (SmC*) phase and the orthogonal (SmA*) phase occur in a narrow temperature range. The new mixtures also have a very long helical pitch in the antiferroelectric phase and a short helical pitch in the ferroelectric phase.

Helicity Control of Circularly Polarized Luminescence from Aromatic Conjugated Copolymers and Their Mixture Using Reversibly Photoinvertible Chiral Liquid Crystals.

We synthesized cyclic chiral compounds [(R)/(S)-D2s] by linking a photoresponsive bisbenzothienylethene (BTE) moiety with an axially chiral binaphthyl moiety. Chiral nematic liquid crystals (N*-LCs) were prepared by adding chiral compounds as dopants to host N-LCs. These N*-LCs exhibited reversible chirality inversion upon photoisomerization between the open and closed forms of the BTE moiety. Here, the mechanism underlying chirality inversion in photoresponsive N*-LCs was investigated by comparing the helical twisting powers (HTPs) of (R)-D2s with those of analogous compounds. It was found that the helical inversion of N*-LCs containing (R)-D2s is governed by a delicate balance between two types of opposite helicity, i.e., the right-handed helicity of the inherently chiral binaphthyl moiety and the left-handed helicity of the BTE moiety bearing intramolecularly induced chirality. Namely, (R)-D2s induced chirality of the BTE moiety, which is attributed to intramolecular chirality transfer from the axially chiral binaphthyl moiety to the BTE moiety. Thus, (R)-D2s are chiral compounds with double chirality consisting of an intrinsically chiral moiety and an intramolecularly induced chiral moiety. Photocontrol of the helical senses and reversible photoinversion of the N*-LCs are achieved by utilizing UV and visible light irradiation and the steric effects of the substituents at the binaphthyl rings in (R)-D2s. In addition, photocontrol of the induced circularly polarized luminescence (CPL) was achieved using the photoinvertible N*-LC. The achiral aromatic conjugated copolymers that exhibited red, green, and blue fluorescence were dissolved and mixed in the present N*-LC, and they exhibited left- and right-handed white CPL with large dissymmetry factors (|glum|) ranging from 0.2 to 1.0. The CPLs were reversibly photoswitched due to photoisomerization between the open and PSS forms of the chiral compounds through UV and visible light irradiation.

One-pot synthesis of azabora[6]helicene by a Schiff base forming reaction.

Azabora[6]helicene as a new heterohelicene analogue was synthesized by a one-pot reaction of commercially available 2,6-diaminopyridine and benzo[c,d]indole-2(1H)-one and subsequent boron coordination. While the single-crystal X-ray diffraction analysis elucidated a helical structure in the solid state, a dynamic helicity inversion was observed in solution.

Unraveling Dynamic Helicity Inversion and Chirality Transfer through the Synthesis of Discrete Azobenzene Oligomers by an Iterative Exponential Growth Strategy.

Unraveling the chirality transfer mechanism of polymer assemblies and controlling their handedness is beneficial for exploring the origin of hierarchical chirality and developing smart materials with desired chiroptical activities. However, polydisperse polymers often lead to an ambiguous or statistical evaluation of the structure-property relationship, and it remains unclear how the iterative number of repeating units function in the helicity inversion of polymer assemblies. Herein, we report the macroscopic helicity and dynamic manipulation of the chiroptical activity of supramolecular assemblies from discrete azobenzene-containing oligomers (azooligomers), together with the helicity inversion and morphological transition achieved solely by changing the iterative chain lengths. The corresponding assemblies also differ from their polydisperse counterparts in terms of thermodynamic properties, chiroptical activities, and morphological control.

Unraveling Dynamic Helicity Inversion and Chirality Transfer through the Synthesis of Discrete Azobenzene Oligomers by an Iterative Exponential Growth Strategy

AbstractUnraveling the chirality transfer mechanism of polymer assemblies and controlling their handedness is beneficial for exploring the origin of hierarchical chirality and developing smart materials with desired chiroptical activities. However, polydisperse polymers often lead to an ambiguous or statistical evaluation of the structure–property relationship, and it remains unclear how the iterative number of repeating units function in the helicity inversion of polymer assemblies. Herein, we report the macroscopic helicity and dynamic manipulation of the chiroptical activity of supramolecular assemblies from discrete azobenzene‐containing oligomers (azooligomers), together with the helicity inversion and morphological transition achieved solely by changing the iterative chain lengths. The corresponding assemblies also differ from their polydisperse counterparts in terms of thermodynamic properties, chiroptical activities, and morphological control.

Selective synthesis of tightly- and loosely-twisted metallomacrocycle isomers towards precise control of helicity inversion motion

Molecular twist is a characteristic component of molecular machines. Selectively synthesising isomers with different modes of twisting and controlling their motion such as helicity inversion is an essential challenge for achieving more advanced molecular systems. Here we report a strategy to control the inversion kinetics: the kinetically selective synthesis of tightly- and loosely-twisted isomers of a trinuclear PdII-macrocycle and their markedly different molecular behaviours. The loosely-twisted isomers smoothly invert between (P)- and (M)-helicity at a rate of 3.31 s–1, while the helicity inversion of the tightly-twisted isomers is undetectable but rather relaxes to the loosely-twisted isomers. This critical difference between these two isomers is explained by the presence or absence of an absolute configuration inversion of the nitrogen atoms of the macrocyclic amine ligand. Strategies to control the helicity inversion and structural loosening motions by the mode of twisting offer future possibilities for the design of molecular machines.

A Single-Enantiomer Emitter Enabled Superstructural Helix Inversion for Upconverting and Downshifting Luminescence with Bidirectional Circular Polarization.

The helical twisting tendency of liquid crystals (LCs) is generally governed by the inherent configuration of the chiral emitter. Here, we introduce the multistage inversion of supramolecular chirality as well as circularly polarized luminescence (CPL) by manipulating the ratio of single enantiomeric emitters (R-PCP) to LC monomers (5CB). Increasing the content of R-PCP from 1 wt % to 3 wt % inverted the helix of LCs from left-handed to right-handed, accompanying a CPL sign changed from positive to negative. The biaxiality of chiral emitters, as well as the steric effect of chiral-chiral and chiral-achiral interaction, were identified as the reasons for helical sense inversion. Due to the strong helical twisting power, 4 wt % R-PCP drove the photonic band gap (PBG) of chiral LCs to match up with their emission range, leading to an inversion of the CPL again with a high dissymmetry factor (≈1.2). Directly adjusting the PBG using chiral emitters is seldom achieved in cholesteric LCs. On this basis, an achiral sensitizer PtTPBP was assembled into the helical superstructure. The generation of triplet-triplet annihilation-induced upconverted CPL from R-PCP and the downshifting CPL from PtTPBP with opposite rotation was achieved in a single chiral LC system by tuning the position of the PBG.

Photoisomerization dynamics of a light-sensitive chiral dopant in a nematic medium

ABSTRACT Azobenzene-based chiral dopants in cholesteric liquid crystals are of interest since the properties they induce in the liquid crystal could be tuned photochemically. Here, we use a substituted binaphthyl with a halogenated azobenzene as a chiral dopant to induce a photoswitchable cholesteric phase in the nematic 4-n-pentyl-4’-cyanobiphenyl. The azobenzene group chemically attached to the chiral dopant undergoes isomerisation from trans to cis upon irradiation with green light (wavelength 535 nm), and from cis to trans upon irradiation with blue light (wavelength 450 nm). The transition between the two isomers causes helicity inversion of the cholesteric, with a left-handed trans isomer and a right-handed cis isomer. We report on the kinetics of photoisomerisation of both processes (trans-to-cis and cis-to-trans) in the nematic host by following the pitch evolution over time. We show that the kinetic mechanism corresponds to a two-step process: a first-order isomerisation followed by a second-order autocatalytic isomerisation. This mechanism differs from the typical first-order kinetics for cis-to-trans or trans-to-cis isomerisation in azobenzenes. The autocatalytic process is attributed to interactions between the chiral dopant and the nematic host.

Macroscopic Helical Assembly of One-Dimensional Coordination Polymers: Helicity Inversion Triggered by Solvent Isomerism.

Assembling macroscopic helices with controllable chirality and understanding their formation mechanism are highly desirable but challenging tasks for artificial systems, especially coordination polymers. Here, we utilize solvents as an effective tool to induce the formation of macroscopic helices of chiral coordination polymers (CPs) and manipulate their helical sense. We chose the Ni/R-,S-BrpempH2 system with a one-dimensional tubular structure, where R-,S-BrpempH2 stands for R-,S-(1-(4-bromophenyl)ethylaminomethylphosphonic acid). The morphology of the self-assemblies can be controlled by varying the cosolvent in water, resulting in the formation of twisted ribbons of R-,S-Ni(Brpemp)(H2O)·H2O (R-,S-2T) in pure H2O; needle-like crystals of R-,S-Ni(Brpemp)(H2O)2·1/3CH3CN (R-,S-1C) in 20 vol % CH3CN/H2O; nanofibers of R-,S-Ni(Brpemp)(H2O)·H2O (R-,S-3F) in 20-40 vol % methanol/H2O or ethanol/H2O; and superhelices of R-,S-Ni(Brpemp)(H2O)·H2O (R-,S-4H or 5H) in 40 vol % propanol/H2O. Interestingly, the helicity of the superhelix can be controlled by using a propanol isomer in water. For the Ni/R-BrpempH2 system, a left-handed superhelix of R-4H(M) was obtained in 40 vol % NPA/H2O, while a right-handed superhelix of R-5H(P) was isolated in 40 vol % IPA/H2O. These results were rationalized by theoretical calculations. Adsorption studies revealed the chiral recognition behavior of these compounds. This work may contribute to the development of chiral CPs with a macroscopic helical morphology and interesting functionalities.

Traveling Perversion as Constant Torque Actuator.

Mechanical stress and conformation of helical elastic rods clamped at both ends were studied upon unwinding. By axial rotation of one end, the winding number was progressively changed from the natural one (n=n_{0}) to complete chirality inversion (n=-n_{0}) while keeping the total elongation fixed and monitoring the applied torque M and tension T. Along the unwinding process, the system crosses three distinct states: natural helix (+), mixed state (+/-), and inverted helix (-). The mixed state involves two helices with opposite chiralities spatially connected by a perversion (helicity inversion). Upon unwinding, the perversion is "injected" (nucleated) from one side and travels toward the opposite side where it is eventually "absorbed" (annihilated), leaving the system in the (-) state. In the mixed state, the profile of M(n) is almost flat: the system behaves as a constant torque actuator. The three states are quantitatively well described in the framework of a biphasic model which neglects the perversion energy and finite size effects. The latter are taken into account in a numerical simulation based on the Kirchhoff theory of elastic rods. The traveling perversion in helical elastic rods and related topological phenomena are universal, with applications from condensed matter to biological and bioinspired systems, including in particular mechanical engineering and soft robotics.

Effect of primary astigmatism on the tight focusing of ellipse field singularities

The tight focusing of ellipse field singularities, namely bright and dark C-points, is studied using the Debye–Wolf diffraction integral in the presence of primary astigmatism. The effect of polarization distribution, the sign of polarization singularity index, amplitude, and handedness of the ellipse field singularities are investigated in the intensity distribution of the focal plane of a high numerical aperture lens system in the presence of primary astigmatism. Ellipse field singularities that are tightly focused can create an additional longitudinal component at the focal plane. At the focal plane, both the longitudinal and transverse components of the ellipse fields are found to be hosted with phase vortices of charge ±1. In the presence of primary astigmatism, the helicity inversion of input C-point does not rotate the focal plane intensity distributions by 180°.

Temperature Directs the Majority-Rules Principle in Supramolecular Copolymers Driven by Triazine-Benzene Interactions.

Supramolecular copolymers have typically been studied in the extreme cases, such as self-sorting or highly mixed copolymer systems, while the intermediate systems have been less understood. We have reported the temperature-dependent microstructure in copolymers of triazine- and benzene-derivatives based on charge-transfer interactions with a highly alternating microstructure at low temperatures. Here, we investigate the temperature-dependent copolymerization further and increase the complexity by combining triazine- and benzene-derivatives with opposite preferred helicities. In this case, intercalation of the benzene-derivative into the triazine-derivative assemblies causes a helical inversion. The inversion of the net helicity was rationalized by comparing the mismatch penalties of the individual monomers, which indicated that the benzene-derivative dictates the helical screw-sense of the supramolecular copolymers. Surprisingly, this was not reflected in further investigations of slightly modified triazine- and benzene-derivatives, thus highlighting that the outcome is a subtle balance between structural features, where small differences can be amplified due to the competitive nature of the interactions. Overall, these findings suggest that the temperature-dependent microstructure of triazine- and benzene-based supramolecular copolymers determines the copolymer helicity of the presented system in a similar way as the mixed majority-rules phenomenon.