Achiral Monomers Research Articles

Interwoven Trimeric Cage-Catenanes with Topological Chirality.

Catenanes have gained increasing attention for their unique features such as topological chirality. To date, the majority of works have focused on catenanes comprising monocyclic rings. Due to the lack of efficient synthetic strategy, catenanes of multiannulated monomers remain scarce. Here, we report the one-pot synthesis of an interwoven trimeric cage-catenane in high yield by dynamic imine condensation between diamine linkers of suitable length and trialdehyde panels in stoichiometry. The formation of cage-catenane is driven by the efficient 6-fold π-π stacking of panels. The monomeric cage and trimeric cage-catenane are interconvertible with reversible imine chemistry, with the latter thermodynamically being more favored. Using a topology-based statistical model, we first reveal that the formation probability of the interwoven catenane surpasses that of its chain-like isomer by 20%. When this pure mathematical model is refined by taking into account the strong template effect provided by the π-π stacking of aromatic panels, it shows that the interwoven structure emerges as the dominant species, almost ruling out the formation of the latter. Although composed of achiral cage monomers, the topological chirality of the interwoven trimeric catenane is unraveled by chiral-high-performance liquid chromatography (HPLC) and circular dichroism (CD) spectroscopy, and single-crystal X-ray diffraction (XRD) analysis of the interwoven cage-catenane also reveals a pair of two topological enantiomers. Our probability analysis-aided rationale would provide a design rationale for guiding the efficient synthesis of topologically sophisticated structures.

Amplification and Attenuation of Asymmetry via Kinetically Controlled Seed-Induced Supramolecular Polymerization.

The amplification of asymmetry in supramolecular polymers has recently garnered significant attention. While asymmetry amplification has predominantly been explored under thermodynamic conditions, the kinetic aspect of this process unveils intriguing observations, yet is scarcely reported in the literature. Herein, drawing inspiration from macromolecular systems, we propose a novel strategy for enhancing asymmetry in supramolecular polymers through a seed-induced supramolecular polymerization approach under kinetic conditions, employing a naphthalene diimide-derived monomer (ANSG) for template-induced supramolecular polymerization, utilizing adenosine triphosphate (ATP) and pyrophosphate (PPi) as templates. A chiral seed comprising [ANSG-ATP]S effectively amplifies the overall supramolecular asymmetry when exposed to a mixture of achiral templates (PPi) and monomers (ANSG), owing to its efficient seeding characteristics under kinetic conditions. As a result of efficient co-operativity, conversely, employing an achiral seed [ANSG-PPi]S in a mixture of chiral templates (ATP) and monomers (ANSG) results in the attenuation of asymmetry, highlighting the effective modulation achievable through the seeding approach, an unprecedented observation in the field. Exploiting the efficient aggregation-induced emission enhancement (AIEE) of the resultant supramolecular polymers further extends the amplification and attenuation of circularly polarized luminescence (CPL) as a potential function.

Simultaneous and in situ syntheses of an enantiomeric pair of homochiral polymers as their perfect stereocomplex in a crystal

Circumventing the issues of conventional stereocomplexation of preformed polymers, herein, we synthesize two enantiopure polymers of opposite chirality simultaneously and in situ as their 1:1 stereocomplex via topochemical polymerization. We design and synthesize an inositol-based achiral monomer for topochemical ene-azide cycloaddition (TEAC) polymerization. In the crystal, the monomer exhibits conformational enantiomerism, and its conformational enantiomers are self-sorted in an arrangement for TEAC polymerization to yield two enantiopure polymers of opposite chirality. Upon heating the monomer crystals, each self-sorted set of conformational enantiomers undergoes regio- and stereospecific polymerization in a single-crystal-to-single-crystal fashion, generating two 1, 4-triazolinyl-linked polymers of opposite chirality simultaneously. The new chiral carbons in all the triazoline rings of a particular polymer chain have the same absolute configuration. These homochiral polymer strands align parallelly, forming a layer, and such enantiopure layers of opposite chirality stack alternately, forming a perfect 1:1 stereocomplex, which we confirmed using single-crystal XRD analysis.

Tunable and Switchable Thermochromism in Cholesteric Liquid Crystalline Elastomers.

Thermochromic materials have found widespread commercial use in packaging as temperature indicators. Often, these products utilize leuco dyes that are mixed into conventional polymeric resins to prepare coatings or films that exhibit temperature-dependent color change. Here, we consider a distinctive approach to thermochromism via the selective reflection of liquid crystalline elastomers that retain the helicoidal structure of the cholesteric phase (CLCEs). Upon heating, the order of the CLCEs reduces and approaches zero, resulting in a change in birefringence as well as material thickness, both of which manifest as changes in the selective reflection to heating. This examination systematically prepares CLCEs capable of reversible thermochromic response as a function of cross-link density and liquid crystalline composition. A particular focus of this examination is the preparation of CLCEs composed of chiral and achiral liquid crystalline monomers that reduce the strength of the mesogen-mesogen interaction and accordingly reduce the nematic-isotropic transition temperature. The low birefringence of some of the CLCE compositions facilitates thermochromic reflection tuning, followed by switching.

Homochiral π‐Rich Covalent Organic Frameworks Enabled Chirality Imprinting in Conjugated Polymers: Confined Polymerization and Chiral Memory from Scratch

AbstractOptically active π‐conjugated polymers (OACPs) have garnered increasing research interest for their resemblance to biological helices and intriguing chirality‐related functions. Traditional methods for synthesizing involve decorating achiral conjugated polymer architectures with enantiopure side substituents through complex organic synthesis. Here, we report a new approach: the templated synthesis of unsubstituted OACPs via supramolecularly confined polymerizations of achiral monomers within nanopores of 2D or 3D chiral covalent organic frameworks (CCOFs). We show that the chiral π‐rich nanospaces facilitate the in situ enantiospecific polymerization and self‐propagation, akin to nonenzymatic polymerase chain reaction (PCR) system, resulting in chiral imprinting. The stacked polymer chains are kinetically inert enough to memorize the chiral information after liberating from CCOFs, and even after treatment at temperature up to 200 °C. The isolated OACPs demonstrate robust enantiodiscrimination, achieving up to 85 % ee in separating racemic amino acids. This underscores the potential of utilizing CCOFs as templates for supramolecularly imprinting optical activity into CPs, paving the way for synthetic evolution and advanced functional exploration of OACPs.

Homochiral π-Rich Covalent Organic Frameworks Enabled Chirality Imprinting in Conjugated Polymers: Confined Polymerization and Chiral Memory from Scratch.

Optically active π-conjugated polymers (OACPs) have garnered increasing research interest for their resemblance to biological helices and intriguing chirality-related functions. Traditional methods for synthesizing involve decorating achiral conjugated polymer architectures with enantiopure side substituents through complex organic synthesis. Here, we report a new approach: the templated synthesis of unsubstituted OACPs via supramolecularly confined polymerizations of achiral monomers within nanopores of 2D or 3D chiral covalent organic frameworks (CCOFs). We show that the chiral π-rich nanospaces facilitate the in situ enantiospecific polymerization and self-propagation, akin to nonenzymatic polymerase chain reaction (PCR) system, resulting in chiral imprinting. The stacked polymer chains are kinetically inert enough to memorize the chiral information after liberating from CCOFs, and even after treatment at temperature up to 200 °C. The isolated OACPs demonstrate robust enantiodiscrimination, achieving up to 85 % ee in separating racemic amino acids. This underscores the potential of utilizing CCOFs as templates for supramolecularly imprinting optical activity into CPs, paving the way for synthetic evolution and advanced functional exploration of OACPs.

Chiral Memory in Dynamic Transformation from Porous Organic Cages to Covalent Organic Frameworks for Enantiorecognition Analysis.

The preservation of chirality during a transformation process, known as the "chiral memory" effect, has garnered significant attention across multiple research disciplines. Here, we first report the retention of the original chiral structure during dynamic covalent chemistry (DCC)-induced structural transformation from porous organic cages into covalent organic frameworks (COFs). A total of six two-dimensional chiral COFs constructed by entirely achiral building blocks were obtained through the DCC-induced substitution of chiral linkers in a homochiral cage (CC3-R or -S) using achiral amine monomers. Homochirality of these COFs resulted from the construction of 3-fold-symmetric benzene-1,3,5-methanimine cores with a propeller-like configuration of one single-handedness throughout the cage-to-COF transformation. The obtained chiral COFs can be further utilized as fluorescence sensors or chiral stationary phases for gas chromatography with high enantioselectivity. The present study thus highlighted the great potential to expand the scope of functional chiral materials via DCC-induced crystal-to-crystal transformation with the chiral memory effect.

The Formation of Supramolecular Chiral Materials from Achiral Molecules Using a Liquid-Crystallin System: Symmetry Breaking, Amplification, and Transfer

Recently, the formation of chiral materials by the self-organization of achiral small molecules has attracted much attention. How can we obtain chirality without a chiral source? Interesting approaches, such as mechanical rotation, circularly polarized light, and asymmetric reaction fields, have been used. We describe recent research developments in supramolecular chirality in liquid crystals, focusing primarily on our group’s experimental results. We present the following concepts in this review. Spontaneous mirror symmetry breaking in self-assembled achiral trimers induces supramolecular chirality in the soft crystalline phase. Two kinds of domains with opposite handedness exist in non-equal populations. The dominant domain is amplified to produce a homochiral state. Chirality is transferred to a polymer film during the polymerization of achiral monomers by using the homochiral state as a template. Finally, we discuss how the concepts obtained from this liquid crystal research relate to the origin of homochirality in life.

Controlling achiral and chiral conformations of benzyl alcohol by ortho-halogenation, collisional relaxation and dimerisation.

Ortho-Halogenated benzyl alcohol can exist in two different low energy chiral conformations, only one of them with an OH-X contact (X = Cl, Br, I). A third, achiral conformation is enabled by the halogen substitution. We show by IR spectroscopy in supersonic jets that the achiral monomer is less stable than the chiral conformation with OH-X contact, but both can be produced in similar amounts using helium as a carrier gas. The robust OH transition observed for the achiral monomer is a sensitive benchmark for the conformational energy sequence, since the chiral conformation without OH-X contact is at least an order of magnitude less abundant, although it is often predicted by DFT to be slightly more stable and separated from the achiral conformation by a low barrier. This competing chiral conformation must be energetically higher by at least a few tenths of a kJ mol-1 to be consistent with experimental observations. That is indeed predicted by high-level energy calculations at the DFT-optimised structures. The most stable dimers of ortho-halogenated benzyl alcohols involve torsionally homo- and heterochiral pairings of the two OH groups, where the hydrogen bond-accepting OH group forms a cooperative intramolecular OH-X contact. The achiral monomer conformation is suppressed in these dimers. A homochiral dimer is formed almost exclusively for Cl, whereas its heterochiral variant is progressively co-stabilised with increasing halogen size. The stretching wavenumber of the donor OH in the dimers depends on the relative chirality of the donor and acceptor conformations. The consistent picture that emerges for Cl, Br and I substitution in ortho-position of benzyl alcohol is discussed in the context of interconversion barriers, heavy atom tunneling, π-π stacking, suppression of OH-π bonding, chirality synchronisation, and shortcomings of DFT approaches in reproducing the observations. The homochiral aggregation preference observed for simple benzyl alcohol is conserved and even enhanced upon ortho-halogenation, albeit partly by different interactions.

Sculpting Mesoscopic Helical Chirality into Covalent Organic Framework Nanotubes from Entirely Achiral Building Blocks

AbstractThe diversification of chirality in covalent organic frameworks (COFs) holds immense promise for expanding their properties and functionality. Herein, we introduce an innovative approach for imparting helical chirality to COFs and fabricating a family of chiral COF nanotubes with mesoscopic helicity from entirely achiral building blocks for the first time. We present an effective 2,3‐diaminopyridine‐mediated supramolecular templating method, which facilitates the prefabrication of helical imine‐linked polymer nanotubes using unprecedented achiral symmetric monomers. Through meticulous optimization of crystallization conditions, these helical polymer nanotubes are adeptly converted into imine‐linked COF nanotubes boasting impressive surface areas, while well preserving their helical morphology and chiroptical properties. Furthermore, these helical imine‐linked polymers or COFs could be subtly transformed into corresponding more stable and functional helical β‐ketoenamine‐linked and hydrazone‐linked COF nanotubes with transferred circular dichroism via monomer exchange. Notably, despite the involvement of covalent bonding breakage and reorganization, these exchange processes overcome thermodynamic disadvantages, allowing mesoscopic helical chirality to be perfectly preserved. This research highlights the potential of mesoscopic helicity in conferring COFs with favourable chiral properties, providing novel insights into the development of multifunctional COFs in the field of chiral materials chemistry.

Sculpting Mesoscopic Helical Chirality into Covalent Organic Framework Nanotubes from Entirely Achiral Building Blocks.

The diversification of chirality in covalent organic frameworks (COFs) holds immense promise for expanding their properties and functionality. Herein, we introduce an innovative approach for imparting helical chirality to COFs and fabricating a family of chiral COF nanotubes with mesoscopic helicity from entirely achiral building blocks for the first time. We present an effective 2,3-diaminopyridine-mediated supramolecular templating method, which facilitates the prefabrication of helical imine-linked polymer nanotubes using unprecedented achiral symmetric monomers. Through meticulous optimization of crystallization conditions, these helical polymer nanotubes are adeptly converted into imine-linked COF nanotubes boasting impressive surface areas, while well preserving their helical morphology and chiroptical properties. Furthermore, these helical imine-linked polymers or COFs could be subtly transformed into corresponding more stable and functional helical β-ketoenamine-linked and hydrazone-linked COF nanotubes with transferred circular dichroism via monomer exchange. Notably, despite the involvement of covalent bonding breakage and reorganization, these exchange processes overcome thermodynamic disadvantages, allowing mesoscopic helical chirality to be perfectly preserved. This research highlights the potential of mesoscopic helicity in conferring COFs with favourable chiral properties, providing novel insights into the development of multifunctional COFs in the field of chiral materials chemistry.

Photoswitchable Enantioselective and Helix-Sense Controlled Living Polymerization.

A pair of enantiomeric photoswitchable PdII catalysts, alkyne-PdII /LR-azo and alkyne-PdII /LS-azo , were prepared via the coordination of alkyne-PdII and azobenzene-modified phosphine ligands LR-azo and LS-azo . Owing to the cis-trans photoisomerization of the azobenzene moiety, alkyne-PdII /LR-azo and alkyne-PdII /LS-azo exhibited different polymerization activities, helix-sense selectivities, and enantioselectivities during the polymerization of isocyanide monomers under irradiation of different wavelength lights. Furthermore, the achiral isocyanide monomer A-1 could be polymerized efficiently using alkyne-PdII /LR-azo under dark condition in a living/controlled manner. Further, it generated single right-handed helical poly-A-1m (LR-azo ), confirmed by the circular dichroism spectra and atomic force microscopy images. However, the polymerization of A-1 almost could not be initiated under 420 nm light in identical conditions of dark condition. Moreover, the photoswitchable catalyst alkyne-PdII /LR-azo exhibited high enantioselectivity for the polymerization of the racemates of L-1 and D-1, respectively. D-1 was polymerized preferentially under dark condition with a D-1/L-1 rate ratio of 70, yielding single right-handed polyisocyanides. Additionally, reversible enantioselectivity was observed under 420 nm light using alkyne-PdII /LR-azo , and the calculated polymerization rate ratio of L-1/D-1 was 57 because of the isomerization of the azobenzene moiety of the catalyst. Furthermore, alkyne-PdII /LS-azo showed opposite enantioselectivity and helix-sense selectivity during the polymerization of the racemates of L-1 and D-1.

Photoswitchable Enantioselective and Helix‐Sense Controlled Living Polymerization

AbstractA pair of enantiomeric photoswitchable PdII catalysts, alkyne‐PdII/LR−azo and alkyne‐PdII/LS−azo, were prepared via the coordination of alkyne‐PdII and azobenzene‐modified phosphine ligands LR−azo and LS−azo. Owing to the cis‐trans photoisomerization of the azobenzene moiety, alkyne‐PdII/LR−azo and alkyne‐PdII/LS−azo exhibited different polymerization activities, helix‐sense selectivities, and enantioselectivities during the polymerization of isocyanide monomers under irradiation of different wavelength lights. Furthermore, the achiral isocyanide monomer A‐1 could be polymerized efficiently using alkyne‐PdII/LR−azo under dark condition in a living/controlled manner. Further, it generated single right‐handed helical poly‐A‐1m(LR−azo), confirmed by the circular dichroism spectra and atomic force microscopy images. However, the polymerization of A‐1 almost could not be initiated under 420 nm light in identical conditions of dark condition. Moreover, the photoswitchable catalyst alkyne‐PdII/LR−azo exhibited high enantioselectivity for the polymerization of the racemates of L‐1 and D‐1, respectively. D‐1 was polymerized preferentially under dark condition with a D‐1/L‐1 rate ratio of 70, yielding single right‐handed polyisocyanides. Additionally, reversible enantioselectivity was observed under 420 nm light using alkyne‐PdII/LR−azo, and the calculated polymerization rate ratio of L‐1/D‐1 was 57 because of the isomerization of the azobenzene moiety of the catalyst. Furthermore, alkyne‐PdII/LS−azo showed opposite enantioselectivity and helix‐sense selectivity during the polymerization of the racemates of L‐1 and D‐1.

Helical polymerisation using a polymer network derived from a blue phase as a template for chirality transfer

ABSTRACT We prepared a blue phase (BP) liquid crystal mixture consisting of a T-shaped nematic liquid crystal, a chiral dopant, a reacting monomer mixture and a photo-initiator. It exhibited a phase sequence of Iso-BPIII-cubic BP-N* on cooling. We produced the polymer stabilised cubic BP (PS-cubic BP) and BPIII (PS-BPIII). After washing low-molar-mass materials from each PS-BP, we obtained the corresponding polymer networks. Marked difference exhibited in a three-dimensional structure between the BPIII and cubic BP polymer networks. Although they were prepared by the photopolymerisation of achiral monomers, they showed optical activities. Furthermore, they proceed the helical polymerisation of achiral reactive monomers to produce a chiral polymer film. The optical handedness of the polymer film is corresponded to that of the original BP. We discuss how the chirality is transferred from each BP to the corresponding polymer film.

Probing Achiral Benzene‐1,3,5‐tricarboxamide Monomers as Inducers of Homochirality in Supramolecular Helical Catalysts**

AbstractAdding a complementary achiral monomer to polymers embedding a mixture of enantiopure monomers (the “sergeants”) and achiral monomers (the “soldiers”) is expected to decrease the optical purity of the polymer main chain. This study reports the influence of such achiral benzene‐1,3,5‐tricarboxamide (BTA) additives on the properties of “sergeants‐and‐soldiers” mixtures composed of an achiral BTA ligand coordinated to copper and of an enantiopure BTA monomer. Whilst N,N’,N’’‐tris(octyl)benzene‐1,3,5‐tricarboxamide (BTA C8) shows no significant improvement in term of enantioselectivity in the catalytic reaction of reference, achiral BTA monomers derived from α,α’‐disubstituted amino esters all lead to an increase in the selectivity at low “sergeant” ratio. This different behaviour was probed by characterizing the coassemblies embedding BTA C8, i. e. the worst‐performing achiral additive, and the BTA derived from the ester of 1‐aminocyclohexane carboxylic acid (BTA Achc), the best‐performing one. Both additives were found to efficiently intercalate with the ligand and the “sergeant” leading to the formation of single helices. However, only the terpolymer embedding BTA Achc appears to be homochiral, accounting for the good enantioselectivity even at very low “sergeant” ratio (0.25 %).

Controlling Helical Asymmetry in Supramolecular Copolymers by In Situ Chemical Modification.

Amplification of asymmetry in complex molecular systems results from a delicate interplay of chiral supramolecular structures and their chemical reactivity. In this work, we show how the helicity of supramolecular assemblies can be controlled by performing a non-stereoselective methylation reaction on comonomers. By methylating chiral glutamic acid side chains in benzene-1,3,5-tricarboxamide (BTA) derivatives to form methyl esters, the assembly properties are modulated. As reacted comonomers, the methyl ester-BTAs induce a stronger bias in the screw-sense of helical fibers predominantly composed of stacked achiral alkyl-BTA monomers. Hence, applying the in situ methylation in a system with the glutamic acid-BTA comonomer induces asymmetry amplification. Moreover, mixing small quantities of enantiomers of glutamic acid-BTA and glutamate methyl ester-BTA in the presence of the achiral alkyl-BTAs leads to deracemization and inversion of the helical structures in solution via the in situ reaction toward a thermodynamic equilibrium. Theoretical modeling suggests that the observed effects are caused by enhanced comonomer interactions after the chemical modification. Our presented methodology enables on-demand control over asymmetry in ordered functional supramolecular materials.

Monomer blended electrochemical polymerization in chiral liquid crystals to produce electro-optically active copolymer

Electro-optically active low-bandgap conjugated copolymers were obtained by electrochemical polymerization (EP) in cholesteric liquid crystal (CLC). We prepared CLC electrolyte mixture blends of monomers, and electrochemically polymerized for obtaining conjugated copolymer with optical activity, in which the structure of the CLC is transferred, from achiral monomers on a CLC template. In addition, this copolymer showed a narrow bandgap and a significant red shift of the absorption band compared to the homopolymer. The optical rotatory dispersion (ORD) indicates that the polymer is chiroptically active and that the optical rotation can be tuned via redox. The guest monomers used for the EP in liquid crystal (LC) require solubility in the host LC and a rod-like structure, limiting their structural design. This technique has the advantage that complex synthesis of monomers is no required, and simple composition of monomers can be used to prepare copolymer films in a convenient manner by blending various monomers. This method expands the design range of optically active electrochromic devices based on conjugated polymers with pleochroic properties.

Fabricating Freestanding, Broadband Reflective Cholesteric Liquid-Crystal Networks via Topological Tailoring of the Sm-Ch Phase Transition.

Numerous biological systems in nature provide much inspiration for humanity to master diverse coloration strategies for creating stimuli-responsive materials and display devices, such as to access gorgeous structural colors from well-defined photonic structures. Cholesteric liquid crystals (CLCs) are a fascinating genre of photonic materials displaying iridescent colors responsive to circumstance changes; however, it is still a big challenge to design materials with broadband color variation as well as good flexibility and freestanding capacity. Herein, we report a feasible and flexible strategy to fabricate cholesteric liquid-crystal networks (CLCNs) with precise colors across the entire visible spectrum through molecular structure tailoring and topology engineering and demonstrate their application as smart displays and rewritable photonic paper. Influences of chiral and achiral LC monomers on the thermochromic behaviors of CLC precursors as well as on the topology of the polymerized CLCNs are systematically investigated, demonstrating that the monoacrylate achiral LC facilitated the formation of a smectic phase-chiral phase (Sm-Ch) pretransitional phase in the CLC mixture and improved the flexibility of the photopolymerized CLCNs. High-resolution multicolor patterns in one CLCN film are generated through photomask polymerization. In addition, the freestanding CLCN films show perceivable mechanochromic behaviors and repeated erasing-rewriting performances. This work opens avenues toward the realization of pixelated colorful patterns and rewritable CLCN films promising in technology fields ranging from information storage and smart camouflage to anti-counterfeiting and smart display.

Rationalizing the Extent of the "Sergeants-and-Soldiers" Effect in Supramolecular Helical Catalysts: Effect of Copper Coordination.

Aggregation of supramolecular helices, for example through interdigitation of their alkyl side chains or through more directional supramolecular interactions, leads to hierarchical architectures with original structural and chiroptical properties. However, when a chiral monomer (the "sergeant") is introduced as a minor component in these assemblies composed of a majority of achiral monomers (the "soldiers"), it is not clear how the aggregation changes the ability of the sergeant to induce a preferential helicity to the polymer main chain (the so-called "sergeants-and-soldiers" effect). This study reports a detailed investigation of the influence of [Cu(OAc)2 ⋅H2 O] coordination on the structure and chiroptical properties of helical hydrogen-bonded co-assemblies composed of a catalytically-active benzene-1,3,5-tricarboxamide (BTA) monomer, acting as the "soldier", and an enantiopure BTA monomer derived from cyclohexylalanine, playing the role of the "sergeant". The copper actually significantly influences the extent of the "sergeants-and-soldiers" effect since it acts as a crosslink that induces some chiral defects in the supramolecular helices. These crosslinks appear to be preserved during the catalytic hydrosilylation of 4-nitroacetophenone. The aggregation of helices through the formation of copper crosslinks is reversible since homochiral single helices are exclusively formed in the case of sergeant-rich assemblies. The fact that both main chain and side chain aggregation affects the chiroptical properties of supramolecular helices must be considered in the design of elaborated chiral materials.

Synthesis of homo polymers and block copolymers of chiral/achiral phenylacetylene derivatives. Spectroscopic and molecular modeling study on solvent‐dependent predominance of helical sense

AbstractA chiral acetylene monomer, (S)‐4‐(2‐butoxy)phenylacetylene [(S)‐1] and an achiral acetylene monomer, 4‐propoxyphenylacetylene (2) were block copolymerized using [(nbd)Rh{C(Ph)=CPh2}(PPh3)]/PPh3 as a catalyst to obtain chiral‐first/achiral‐second and achiral‐first/chiral‐second block copolymers, poly[(S)‐1]‐block‐poly(2) and poly(2)‐block‐poly[(S)‐1]. The block copolymers exhibited circular dichroism (CD) signals in THF attributable to helical conformation with predominantly one‐handed screw sense originating from the poly[(S)‐1] block. In CHCl3, the block copolymers exhibited CD signals with signs reversed from those in THF. The conformational stability of the copolymers was dependent on the composition of (S)‐1 units, regardless of the feed order of the chiral and achiral monomers. The solvent‐dependent predominance of helical sense was confirmed by the molecular dynamics (MD) simulations of poly[(S)‐1] 32‐mer models.