Hole polarons in pure BaTiO3 studied by computer modeling

Self‐trapped hole polarons in technologically important perovskite‐type ceramic of BaTiO₃ have been modeled by means of the quantum chemical method modified for crystal calculations. The computations are carried out in the self‐consistent field (SCF) manner using the embedded molecular cluster model. The spatial configuration of a hole polaron, displacement of defect‐surrounding atoms, and wave functions of the polaron ground and excited states are obtained and analyzed. The probability of spontaneous hole self‐trapping is estimated in the perfect lattice of the BaTiO₃ crystal by calculating the value of the hole self‐trapping energy as a difference of the atomic relaxation energy and the hole localization energy. This value is found to be negative, −1.49 eV, which demonstrates the preference of the self‐trapped polaron state. The calculated polaron absorption energy, 0.5 eV, is discussed in light of the available experimental data. © 2000 John Wiley & Sons, Inc. Int J Quant Chem 79: 358–366, 2000     

Particle plasmon‐induced charge trapping at heterointerfaces in PCDTBT:PC70BM blends

We investigate the influence of particle plasmons on exciton and charge generation and recombination processes in the blend of poly (9‐(1‐octylnonyl)‐9H‐carbazole‐benzothiadiazole‐4,7‐diyl‐2,5‐thiophenediyl) (PCDTBT) and [6,6]‐phenyl‐C₇₀butyric acid methyl ester (PC₇₀BM). The particle plasmons are generated from gold nanoparticles, which are embedded into PCDTBT:PC₇₀BM blend. For the blend with gold nanoparticles, we observe enhance light harvesting. Despite the enhanced light collection, we find that the quasi‐steady‐state charge generation has not been influenced by the particle plasmons. However, the generation and recombination of long‐lived (sub‐millisecond) polaron paris have been significantly enhanced: from untrapped state in the pristine blend to the trapped state in the gold nanoparticle‐embedded blend. This result implies that the plasmon‐influenced polarons are trapped at the broadband geminate polaron pair (GPP) state. This state acts as an intermediate state, which either leads to the formation of charge transfer excitons (CTXs) or free charge carriers. In our case, the particle plasmon‐influenced polarons are trapped in the GPP state, which leads to the formation of CTXs. For this reason, we do not observe the enhanced charge generation in PCDTBT:PC₇₀BM blend with particle plasmon resonance. Finally, we revealed that the long‐lived polarons mainly resulted from the localization by particle plasmons. The macroscopic modification in the blend film made negligible contributions to this influence. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 940–947     

Effect of magnetic exchange,double exchange,vibronic coupling,and asymmetry on magnetic properties in d2–d3 mixed‐valence dimers

The effect of magnetic exchange, double exchange, vibronic coupling, and asymmetry on magnetic properties of d²–d³ systems is discussed. The temperature‐dependent magnetic moment was calculated with the semiclassical adiabatic approach. The results show that the vibronic coupling from the out‐of‐phase breathing vibration on the metal sites (Piepho, Krausz, and Schatz [PKS] model) and the vibronic coupling from the stretching vibration between the metal sites (P model) favor the localization and delocalization of the “extra” electron in mixed‐valence dimers, respectively. The magnetic properties are determined by the interplay among magnetic exchange, double exchange, and vibronic coupling. The results obtained by analyzing d²–d³ systems can be generalized to other full delocalized dinuclear mixed valence systems with a unique transferable electron. © 2005 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Stationary polarons in discrete molecular chains

Properties of the large acoustic polarons in discrete molecular chains have been investigated within the adiabatic approximation. It turns out that practically all the polaron features are determined by the single parameter‐coupling constant which represents the ratio between the small polaron binding energy and the electron bandwidth. Three different types of stationary solutions were found corresponding to weak, intermediate, and strong coupling limits, respectively. In the weak coupling regime, that is, for the values of coupling constant exceeding the limit of the applicability of continuum approximation but lower than the critical one ( $g_C$ ), we observe symmetric bond‐centered solution corresponding to the polaron positioned in the middle between the adjacent lattice sites. When coupling constant overgrows, this critical value transition toward the site‐centered state occurs. It takes place continuously through the intermediate asymmetric state whose position gradually approaches lattice site as coupling constant increases. One of the main consequences of the lattice discreteness is the emergence of the periodic potential, Peierls‐Nabarro potential relief, through which polarons have to pass to transfer along the chain. The conditions for the polaron propagation are formulated in terms of the threshold velocity. © 2012 Wiley Periodicals, Inc.     

A facile preparation method for synthesis of silica sulfuric acid/poly(o‐methoxyaniline) core–shell nanocomposite

A new nanocomposite of poly(o‐methoxyaniline) (POMA) is introduced by overlayer formation of POMA on silica. The key appealing feature of the synthesis is the role of silica sulfuric acid (SSA) both as solid acid dopant and template in overlayer self‐assembly of POMA on silica surface. Hereon siloxide group (Si―O^?) of silica surface is replaced with dopant anion of SSA (≡Si―O―SO₃^?), which leads to formation of a overlayer of POMA on the silica surface. The composite particles are spherical in the nanoscale range of 50 nm without application of any external template (no‐template synthesis). Nanocomposite was fully characterized by various instrumentation methods: Fourier transform infrared (FT‐IR), ultraviolet–visible (UV–vis), thermogravimetric analysis (TGA), diffrential thermal analysis (DTA), elemental analysis (CHNS), energy dispersive X‐ray (EDX), X‐ray photoelectron spectroscopy (XPS) and X‐ray difraction (XRD). Based on XPS and CHNS results, it is demonstrated that the doping level of POMA is as high as 50% and for the first time the ratio of 4:2:2 is obtained for ―NH― (amine): ―HN^.+― (polarons): ?HN⁺― (bipolarons), respectively. In fact, bipolarons may also coexist with polarons with a 1:1 ratio of them. Moreover, the synthesis benefits from the perspective of green chemistry which is preparation under solid‐state (solvent‐free) condition. Copyright © 2015 John Wiley & Sons, Ltd.     

Unambiguous Diagnosis of Photoinduced Charge Carrier Signatures in a Stoichiometrically Controlled Semiconducting Polymer‐Wrapped Carbon Nanotube Assembly

Single‐walled carbon nanotube (SWNT)‐based nanohybrid compositions based on (6,5) chirality‐enriched SWNTs ([(6,5) SWNTs]) and a chiral n‐type polymer (S‐PBN(b)‐Ph₄PDI) that exploits a perylenediimide (PDI)‐containing repeat unit are reported; S‐PBN(b)‐Ph₄PDI‐[(6,5) SWNT] superstructures feature a PDI electron acceptor unit positioned at 3 nm intervals along the nanotube surface, thus controlling rigorously SWNT–electron acceptor stoichiometry and organization. Potentiometric studies and redox‐titration experiments determine driving forces for photoinduced charge separation (CS) and thermal charge recombination (CR) reactions, as well as spectroscopic signatures of SWNT hole polaron and PDI radical anion (PDI^?.) states. Time‐resolved pump–probe spectroscopic studies demonstrate that S‐PBN(b)‐Ph₄PDI‐[(6,5) SWNT] electronic excitation generates PDI^?. via a photoinduced CS reaction (τ_CS≈0.4 ps, Φ_CS≈0.97). These experiments highlight the concomitant rise and decay of transient absorption spectroscopic signatures characteristic of the SWNT hole polaron and PDI^?. states. Multiwavelength global analysis of these data provide two charge‐recombination time constants (τ_CR≈31.8 and 250 ps) that likely reflect CR dynamics involving both an intimately associated SWNT hole polaron and PDI^?. charge‐separated state, and a related charge‐separated state involving PDI^?. and a hole polaron site produced via hole migration along the SWNT backbone that occurs over this timescale.     

Atom transfer radical polymerization of n‐butyl acrylate catalyzed by CuBr/N‐(n‐hexyl)‐2‐pyridylmethanimine

The homogeneous atom transfer radical polymerization (ATRP) of n‐butyl acrylate with CuBr/N‐(n‐hexyl)‐2‐pyridylmethanimine as a catalyst and ethyl 2‐bromoisobutyrate as an initiator was investigated. The kinetic plots of ln([M]₀/[M]) versus the reaction time for the ATRP systems in different solvents such as toluene, anisole, N,N‐dimethylformamide, and 1‐butanol were linear throughout the reactions, and the experimental molecular weights increased linearly with increasing monomer conversion and were very close to the theoretical values. These, together with the relatively narrow molecular weight distributions (polydispersity index ～ 1.40 in most cases with monomer conversion > 50%), indicated that the polymerization was living and controlled. Toluene appeared to be the best solvent for the studied ATRP system in terms of the polymerization rate and molecular weight distribution among the solvents used. The polymerization showed zero order with respect to both the initiator and the catalyst, probably because of the presence of a self‐regulation process at the beginning of the reaction. The reaction temperature had a positive effect on the polymerization rate, and the optimum reaction temperature was found to be 100 °C. An apparent enthalpy of activation of 81.2 kJ/mol was determined for the ATRP of n‐butyl acrylate, corresponding to an enthalpy of equilibrium of 63.6 kJ/mol. An apparent enthalpy of activation of 52.8 kJ/mol was also obtained for the ATRP of methyl methacrylate under similar reaction conditions. Moreover, the CuBr/N‐(n‐hexyl)‐2‐pyridylmethanimine‐based system was proven to be applicable to living block copolymerization and living random copolymerization of n‐butyl acrylate with methyl methacrylate. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3549–3561, 2002     

Charge Carrier Transport Mechanism in Ta2O5, TaON,and Ta3N5 Studied by Applying Polaron Hopping and Bandlike Models

TaON and Ta₃N₅ are considered promising materials for photocatalytic and photoelectrochemical water splitting. In contrast, their counterpart Ta₂O₅ does not exhibit good photocatalytic performance. This may be explained with the different charge carrier transport mechanisms in these materials, which are not well understood yet. Herein, we investigate the charge transport properties in Ta₂O₅, TaON, and Ta₃N₅ by polaron hopping and bandlike models. First, the polaron binding energies were calculated to evaluate whether the small polaron occurs in these materials. Then we performed calculations to localize the excess carriers as small polarons using a hybrid density functional. We find that the small polaron hopping is the charge transfer mechanism in Ta₂O_5, whereas our calculations indicate that this mechanism may not occur in TaON and Ta₃N₅. We also investigated the bandlike model mechanism by calculating the charge carrier mobility of these materials using the effective mass approximation, but the calculated mobility is not consistent with experimental results. This study is a first step towards understanding charge transport in oxynitrides and nitrides and furthermore establishes a simple rule to determine whether a small polaron occurs in a material.     

Parallel implementation of γ‐point pseudopotential plane‐wave DFT with exact exchange

Semi‐local functionals commonly used in density functional theory (DFT) studies of solids usually fail to reproduce localized states such as trapped holes, polarons, excitons, and solitons. This failure is ascribed to self‐interaction which creates a Coulomb barrier to localization. Pragmatic approaches in which the exchange correlation functionals are augmented with small amount of exact exchange (hybrid‐DFT, e.g., B3LYP and PBE0) have shown to promise in rectifying this type of failure, as well as producing more accurate band gaps and reaction barriers. The evaluation of exact exchange is challenging for large, solid state systems with periodic boundary conditions, especially when plane‐wave basis sets are used. We have developed parallel algorithms for implementing exact exchange into pseudopotential plane‐wave DFT program and we have implemented them in the NWChem program package. The technique developed can readily be employed in Γ‐point plane‐wave DFT programs. Furthermore, atomic forces and stresses are straightforward to implement, making it applicable to both confined and extended systems, as well as to Car‐Parrinello ab initio molecular dynamic simulations. This method has been applied to several systems for which conventional DFT methods do not work well, including calculations for band gaps in oxides and the electronic structure of a charge trapped state in the Fe(II) containing mica, annite. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010     

Synthesis,structural, and retrostructural analysis of helical dendronized poly(1‐naphthylacetylene)s

Structural and retrostructural analysis of chiral, nonracemic ( poly [(3,4,5)dm8G1‐1EN] ), and achiral ( poly[(3,4,5)12G1‐1EN] ) poly(1‐naphthylacetylene)s demonstrates new design principles for helical dendronized polyarylacetylenes. The oblate cylindrical dendronized polymers self‐organize in a c2mm centered rectangular columnar (Φ_r‐c) lattice. An all cis‐polyene backbone microstructure with very high cisoid character is introduced to rationalize features from small‐ and wide‐angle X‐ray diffraction experiments. More compact helical conformations are ideal for efficient communication or amplification of chirality over long distances. Peripheral chiral tails select a preferred helical screw sense of the polyene backbone. In solution, the preferred helical conformation persists over a wide temperature range. In bulk, the naphthyl moiety facilitates a longer correlation length for helical order compared to an analogous minidendritic poly(phenylacetylene). These attributes suggest that the naphthyl moiety may be better suited for expressing helical chirality in monolayer domains. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4974–4987, 2007     

Organotin mefenamic complexes—preparations,spectroscopic studies and crystal structure of a triphenyltin ester of mefenamic acid: novel anti‐tuberculosis agents

The triphenyltin adduct of mefenamic acid, [SnPh₃L] ( 1 ), the monophenyltin complex [PhSnOL] _n ( 2 ), and the dibutyltin complex [SnBu₂L₂] (3), where HL is 2‐[bis(2,3‐dimethylphenyl)amino]benzoic acid (mefenamic acid), have been prepared and structurally characterized by means of vibrational, ¹H and ¹³C NMR spectroscopies. The crystal structure of 1 has been determined by X‐ray crystallography. X‐ray analysis revealed a pseudo‐pentacoordinated structure containing Ph₃Sn coordinated to the carboxylato group. The structural distortion is a displacement from the tetrahedron toward the trigonal bipyramid. Significant C? H–π interactions and intramolecular hydrogen bonds stabilize the structure 1. The polar imino hydrogen atom participates in intramolecular hydrogen bonds. Complex 1 is self‐assembled via C? H–π and stacking interactions. Vibrational and NMR data are discussed in terms of the crystal structure and the proposed structures for 1–3. Compounds 1 and 3 were tested for antimycobacterial activity against Mycobacterium tuberculosis H37Rv. Copyright © 2002 John Wiley & Sons, Ltd.     

A theoretical study of electronic effects in alkyne‐linked reactive intermediates: (nitrenoethynyl)methylenes, (nitrenoethynyl)silylenes,and (nitrenoethynyl)germylenes

Acetylene‐linked reactive intermediates of (nitrenoethynyl)‐X‐methylenes, (nitrenoethynyl)‐X‐silylenes, and (nitrenoethynyl)‐X‐germylenes are almost experimentally unreachable (X–M–C≡C–N; X=H ( 1 ), CN ( 2 ), OH ( 3 ), NH₂ ( 4 ), NO₂ ( 5 ), and CHO ( 6 ); M=C, Si, and Ge). The effects of the electron‐donating and electron withdrawing groups were compared and contrasted at seven levels of theory. All singlet species as ground states with one local open‐shell singlet carbene subunit (π¹π¹) and another local open‐shell singlet nitrene subunit (π¹π¹) were found to be more stable than their corresponding triplets including one local open‐shell singlet carbene (δ¹π¹) (or one local closed‐shell singlet carbene [δ²π⁰]) and another local triplet nitrene subunit (π¹π¹) with 45.94–77.996 kcal/mol singlet–triplet energy gap (ΔE_s‐t). Their relative silylenes and germylenes made reduction of ΔE_s‐t, so the triplet ground states were found for species 3 _Si , 4 _Si , 5 _Si , 2 _Ge , 3 _Ge , 4 _{Ge ,} and 5 _Ge . All the singlet silylenes/germylenes formed by one local closed‐shell singlet silylenes/germylenes (δ²π⁰) and one local closed‐shell singlet nitrene subunit (π²π⁰). Also, one local closed‐shell singlet silylene/germylene subunit (δ²π⁰) and one local triplet nitrene subunit (π¹π¹) were observed for triplet silylenes/germylenes. The singlet and triplet species 3 _Si , 4 _Si , 3 _Ge , and 4 _Ge , due to their electrophilic (Si₄/Ge₄) and nucleophilic (X₅) centers, could be identified as intermediates in chemical reactions.     

Toward assessment of density functionals for vibronic coupling in two‐photon absorption: A case study of 4‐nitroaniline

In this study, we predict vibronic two‐photon absorption (TPA) spectra for 4‐nitroaniline in vacuo. The simulations are performed using density functional theory and the approximate second‐order coupled‐cluster singles and doubles model CC2. Thereby we also demonstrate the possibility of simulations of vibronic TPA spectra with ab initio wavefunction methods that include electron correlation for medium‐sized systems. A special focus is put on the geometric derivatives of the second‐order transition moment and the dipole moment difference between the charge‐transfer excited state and the ground state. The results of CC2 calculations bring new insight into the vibronic coupling mechanism in TPA spectra of 4‐nitroniline and demonstrate that the mixed term is quite large and that it also exhibits a negative interference with the Franck‐Condon contribution. © 2015 Wiley Periodicals, Inc.     

Synthesis,Characterization, and Crystal Structure of a Metallamacrocycle

The novel macrocyclic decanuclear manganese(III) 30‐metallacrown‐10 compound [Mn₁₀(RS‐3‐chmshz)₁₀(DMF)₁₀] · 9DMF ( 1 ) was synthesized by self‐assembly and characterized (H₃RS‐3‐chmshz = N‐((R,S)‐3‐cyclohexenoyl)‐5‐methylsalicylhydrazide). Compound 1 is a 30‐membered decanuclear metallamacrocycle and crystallizes in triclinic space group P2₁/c, in an alternating …ΔΛΔΛ…‐type chiral configuration. The decanuclear systems measure ~2.6 nm in diameter and ~1.1 nm in thickness. The racemic N‐(R,S)‐3‐cyclohexenoyl group directing into the cavity of the metallamacrocycle shows the alternate R,S chiral configuration. Magnetic measurements on the title 30‐metallacrown‐10 compound show weak antiferromagnetic exchange interaction.     

All‐electron relativistic computations on the low‐lying electronic states,bond length,and vibrational frequency of CeF diatomic molecule with spin–orbit coupling effects

Ab initio all‐electron computations have been carried out for Ce⁺ and CeF, including the electron correlation, scalar relativistic, and spin–orbit coupling effects in a quantitative manner. First, the n‐electron valence state second‐order multireference perturbation theory (NEVPT2) and spin–orbit configuration interaction (SOCI) based on the state‐averaged restricted active space multiconfigurational self‐consistent field (SA‐RASSCF) and state‐averaged complete active space multiconfigurational self‐consistent field (SA‐CASSCF) wavefunctions have been applied to evaluations of the low‐lying energy levels of Ce⁺ with [Xe]4f¹5d¹6s¹ and [Xe]4f¹5d² configurations, to test the accuracy of several all‐electron relativistic basis sets. It is shown that the mixing of quartet and doublet states is essential to reproduce the excitation energies. Then, SA‐RASSCF(CASSCF)/NEVPT2 + SOCI computations with the Sapporo(‐DKH3)‐2012‐QZP basis set were carried out to determine the energy levels of the low‐lying electronic states of CeF. The calculated excitation energies, bond length, and vibrational frequency are shown to be in good agreement with the available experimental data. © 2018 Wiley Periodicals, Inc.     

Synthesis,molecular, and morphological characterization of initial and modified diblock copolymers with organic acid chloride derivatives

Six well defined PS‐b‐PB_1,2 diblock copolymers (PS: polystyrene and PB: polybutadiene) with almost 100% of 1,2 microstructure for the PB segment were synthesized. Size exclusion chromatography (SEC), membrane osmometry (MO) and proton nuclear magnetic resonance spectroscopy (¹H NMR) were used for verification of the molecular characteristics and the 100% ‐1,2 addition for the PB blocks. Modification with heptanoyl or pentadecafluorooctanoyl chloride was accomplished via hydroboration and subsequent oxidation, leading to hydroxylated PB blocks and was verified with ¹H NMR and Fourier transform infrared (FTIR) spectroscopy. Only two samples were modified with both organic acid chloride derivatives. Structural characterization was accomplished via transmission electron microscopy (TEM) and small‐angle X‐ray scattering (SAXS) in all cases. The self‐assembly was more evident in the modified copolymers with the corresponding halides due to the increase of the molecular weight of the modified PB block. Taking into consideration the χN values in each case and comparing the results with those of PS‐b‐PI copolymers already reported in the literature the discrepancies with the theoretical predictions are very small or minimal. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Synthesis,structural analysis,and visualization of poly(2‐ethynyl‐9‐substituted carbazole)s and poly(3‐ethynyl‐9‐substituted carbazole)s containing chiral and achiral minidendritic substituents

The synthesis of 2‐ethynyl‐9‐substituted carbazole and 3‐ethynyl‐9‐substituted carbazole monomers containing first‐generation chiral and achiral dendritic (i.e., minidendritic) substituents, 2‐ethynyl‐9‐[3,4,5‐tris(dodecan‐1‐yloxy)benzyl]carbazole (2ECz), 3‐ethynyl‐9‐[3,4,5‐tris(dodecan‐1‐yloxy)benzyl]carbazole (3ECz), 2‐ethynyl‐9‐{3,4,5‐tris[(S)‐2‐methylbutan‐1‐yloxy]benzyl}carbazole (2ECz*), and 3‐ethynyl‐9‐{3,4,5‐tris[(S)‐2‐methylbutan‐1‐yloxy]benzyl}carbazole (3ECz*), is presented. All monomers were polymerized and copolymerized by stereospecific polymerization to produce cis‐transoidal soluble stereoisomers. A structural analysis of poly(2ECz), poly(2ECz*), poly(3ECz), poly(3ECz*), poly(2ECz*‐co‐2ECz), and poly(3ECz*‐co‐3ECz) by a combination of techniques, including ¹H NMR, ultraviolet–visible, and circular dichroism spectroscopy, thermal optical polarized microscopy, and X‐ray diffraction experiments, demonstrated that these polymers had a helical conformation that produced cylindrical macromolecules exhibiting chiral and achiral nematic phases. Individual chains of these cylindrical macromolecules were visualized by atomic force microscopy. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3509–3533, 2002     

Photoresponsive hyaluronate nanogel as an anticancer drug carrier

In this study, we introduced photolabile 4‐(4‐(1‐hydroxyethyl)‐2‐methoxy‐5‐nitrophenoxy)butyric acid (HMNB) to prepare photoresponsive nanogels. Hyaluronate (HA) grafted with 4‐(4‐(1‐hydroxyethyl)‐2‐methoxy‐5‐nitrophenoxy)butyric acid (HA‐g‐HMNB) was self organized in aqueous solution. Interestingly, HA‐g‐HMNB nanogels exhibited caging and photo‐uncaging properties for an encapsulated antitumor drug. Photoactivation allowed accelerated antitumor drug release from uncaged nanogels. We found a significant improvement in KB tumor‐cell‐killing efficacy when this system was associated with local light irradiation. Copyright © 2013 John Wiley & Sons, Ltd.     

Homopolymerizations and random copolymerizations of olefins with amino‐substituted cyclopentadienylchromium complexes

1‐(2‐N,N‐Dimethylaminoethyl)‐2,3,4,5‐tetramethylcyclopentadienyl‐chromium dichloride ( 1 ), (2‐N,N‐dimethylaminoethyl)cyclopentadienylchromium dichloride ( 6 ), and (2‐N,N‐dimethylaminoethyl)indenylchromium dichloride ( 7 ) in the presence of modified methylaluminoxane exhibit high catalytic activities for the polymerization of ethylene with random copolymerizations of ethylene with propylene, ethylene with 1‐hexene, and propylene with 1‐hexene. These initiators conduct polymerizations to give high molecular weight polymers with low polydispersities. However, the stereoregularities are very poor in these reactions. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 2759–2771, 2002     

Mirror helices and helicity switch at surfaces based on chiral triangular-shape oligo(phenylene ethynylenes)

The self‐assembly of triangular‐shaped oligo(phenylene ethynylenes) (OPEs), peripherally decorated with chiral and linear paraffinic chains, is investigated in bulk, onto surfaces and in solution. Whilst the X‐ray diffraction data for the chiral studied systems display a broad reflection centered at 2θ ～20° (λ=Cu_Kα), the higher crystallinity of OPE 3 , endowed with three linear decyl chains, results in a diffractrogram with a number of well‐resolved reflections that can be accurately indexed as a columnar packing arranged in 2D oblique cells. Compounds (S)‐ 1 a and (R)‐ 1 b —endowed with (S)‐ and (R)‐3,7‐dimethyloctyloxy chains—transfer their chirality to the supramolecular structures formed upon their self‐assembly, and give rise to helical nanostructures of opposite handedness. A helicity switch is noticeable for the case of chiral (S)‐ 2 decorated with (S)‐2‐methylnonyloxy chains which forms right‐handed helices despite it possesses the same stereoconfiguration for their stereogenic carbons as (S)‐ 1 a that self‐assembles into left‐handed helices. The stability and the mechanism of the supramolecular polymerization in solution have been investigated by UV/Vis experiments in methylcyclohexane. These studies demonstrate that the larger the distance between the stereogenic carbon and the aromatic framework is, the more stable the aggregate is. Additionally, the self‐assembly mechanism is conditioned by the peripheral substituents: whereas compounds (S)‐ 1 a and (R)‐ 1 b self‐assemble in a cooperative manner with a low degree of cooperativity, the aggregation of (S)‐ 2 and 3 is well described by an isodesmic model. Therefore, the interaction between the chiral coil chains conditions the handedness of the helical pitch, the stability of the supramolecular structure and the supramolecular polymerization mechanism of the studied OPEs.