Liquid crystalline supramolecular crosslinked polymer complexes of ditopic rylenebisimides and P4VP

Perylenebisimide and naphthalenebisimide (PBI‐PDP and NBI‐PDP) end functionalized with pentadecyl phenol is designed as ditopic hydrogen bonding acceptors to form supramolecular crosslinked network with poly(4‐vinyl pyridine) (P4VP). The pristine PBI‐PDP has been grown as single crystals from DCM‐MeOH (dichloromethane‐methanol) mixture at room temperature, which revealed a P21 space group. Noticeably, the pentadecyl alkyl chain shields the aromatic perylene core on both sides resulting in the absence of π–π interaction in single‐crystal assembly. The naphthalenebisimide derivative exhibits thermotropic liquid crystalline behavior, while both the molecules exhibits lyotropic liquid crystalline phases in tetrahydrofuran (THF), which were characterized using a combination of differential scanning calorimeter, X‐ray diffraction, and polarized light microscopy. The hydrogen‐bonded complex of both the rylenebisimides with P4VP preserves the mesomorphic properties in THF. The electron transport mobility measured by space charge limited current measurements reveals a two orders of magnitude increase in the charge transport in the P4VP complex compared to that of the pristine molecule. The average electron mobility obtained is μ _e,avg: 10^?3 cm²/Vs for P4VP‐PBI compared to μ _e,avg: 10^?5 cm²/Vs for pristine PBI derivative. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55 , 951–959     

Self‐assembled complexes of poly(acrylic acid) and poly(styrene)‐block‐poly(4‐vinyl pyridine)

Polymer complexes were prepared from high molecular weight poly(acrylic acid) (PAA) and poly(styrene)‐block‐poly(4‐vinyl pyridine) (PS‐b‐P4VP) in dimethyl formamide (DMF). The hydrogen bonding interactions, phase behavior, and morphology of the complexes were investigated using Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), dynamic light scattering (DLS), atomic force microscopy (AFM), and transmission electron microscopy (TEM). In this A‐b‐B/C type block copolymer/homopolymer system, P4VP block of the block copolymer has strong intermolecular interaction with PAA which led to the formation of nanostructured micelles at various PAA concentrations. The pure PS‐b‐P4VP block copolymer showed a cylindrical rodlike morphology. Spherical micelles were observed in the complexes and the size of the micelles increased with increasing PAA concentration. The micelles are composed of hydrogen‐bonded PAA/P4VP core and non‐bonded PS corona. Finally, a model was proposed to explain the microphase morphology of complex based on the experimental results obtained. The selective swelling of the PS‐b‐P4VP block copolymer by PAA resulted in the formation of different micelles. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1192–1202, 2009     

Synthesis of poly(2‐vinyl pyridine)‐b‐poly(n‐hexyl isocyanate) amphiphilic coil‐rod block copolymer by anionic polymerization

A well‐defined amphiphilic coil‐rod block copolymer, poly(2‐vinyl pyridine)‐b‐poly(n‐hexyl isocyanate) (P2VP‐b‐PHIC), was synthesized with quantitative yields by anionic polymerization. A low reactive one‐directional initiator, potassium diphenyl methane (DPM‐K), was very effective in polymerizing 2‐vinyl pyridine (2VP) without side reactions, leading to perfect control over molecular weight and molecular weight distribution over a broad range of initiator and monomer concentration. Copolymerization of 2VP with n‐hexyl isocyanate (HIC) was carried out in the presence of sodium tetraphenyl borate (NaBPh₄) to prevent backbiting reactions during isocyanate polymerization. Terminating the living end with a suitable end‐capping agent resulted in a P2VP‐b‐PHIC coil‐rod block copolymer with controlled molecular weight and narrow molecular weight distribution. Cast film from a chloroform solution of P2VP‐b‐PHIC displayed microphase separation, characteristic of coil‐rod block copolymers. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 607–615, 2005     

Competitive hydrogen bonding and self‐assembly in poly(2‐vinyl pyridine)‐block‐poly(methyl methacrylate)/poly(hydroxyether of bisphenol A) blends

Blends of poly(2‐vinyl pyridine)‐block‐poly(methyl methacrylate) (P2VP‐b‐PMMA) and poly(hydroxyether of bisphenol A) (phenoxy) were prepared by solvent casting from chloroform solution. The specific interactions, phase behavior and nanostructure morphologies of these blends were investigated by Fourier transform infrared (FTIR) spectroscopy, differential scanning calorimetry (DSC), dynamic light scattering (DLS), atomic force microscopy (AFM), and transmission electron microscopy (TEM). In this block copolymer/homopolymer blend system, it is established that competitive hydrogen bonding exists as both blocks of the P2VP‐b‐PMMA are capable of forming intermolecular hydrogen bonds with phenoxy. It was observed that the interaction between phenoxy and P2VP is stronger than that between phenoxy and PMMA. This imbalance in the intermolecular interactions and the repulsions between the two blocks of the diblock copolymer lead to a variety of phase morphologies. At low phenoxy concentration, spherical micelles are observed. As the concentration increases, PMMA begins to interact with phenoxy, leading to the changes of morphology from spherical to wormlike micelles and finally forms a homogenous system. A model is proposed to describe the self‐assembled nanostructures of the P2VP‐b‐PMMA/phenoxy blends, and the competitive hydrogen bonding is responsible for the morphological changes. © 2009 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 47: 1894–1905, 2009     

Morphological change of a diblock copolymer film induced by selective doping of a photoactive chromophore

Tetrakis‐5,10,15,20‐(4‐carboxyphenyl)porphyrine (TCPP) was position‐selectively introduced into a diblock copolymer film of polystyrene‐block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) with a sea–island microphase structure. By immersing the PS‐b‐P4VP film into a solution of TCPP/methanol, TCPP was introduced into the island parts comprising P4VP phase. The morphology of the island parts depended on the immersion time and TCPP concentration. A schematic model for the morphological change caused by the phase‐selective introduction of TCPP was proposed. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 368–375, 2007     

Supramolecular Complex of Poly(styrene)-b-Poly(4-vinylpyridine) and 1-Pyrenebutyric Acid in Thin Film

Summary: Here, we have described a novel supramolecular complex (SMC) between poly(styrene)-b-poly(4-vinylpyridine) (PS-b-P4VP) and 1-pyrenebutyric acid (PBA) and studied of its self assembly in thin film. PBA will make supramolecular complex with the P4VP block due to strong hydrogen bonding between the carboxylic group of 1-pyrenebutyric acid and pyridine ring of P4VP. The formation of supramolecular complex between PS-P4VP and PBA through hydrogen bonding is investigated through FTIR study. The supramolecular complex of PS-b-P4VP and 1-pyrenebutyric acid changed the block copolymer morphology from cylindrical to lamella in thin film due to the increase of the volume fraction of P4VP (PBA). In both cases (parent block copolymer and SMC), the microdomains are oriented normal to the substrate after annealing in a selective solvent. Pure block copolymer shows cylindrical morphology with a periodicity of ∼26 nm, whereas the SMC shows lamellar morphology with a periodicity of ∼ 29 nm. After fabricating the thin film from SMC, 1-pyrenebutyric acid can be easily removed by dissolving the thin film in ethanol to transform the block copolymer thin film into nanotemplate or membrane.     

Fabrication of polymeric nano-objects using PS5P2VP5 heteroarm star copolymers as building elements

This work is focused on the self-organization of an heteroarm star copolymer consisting of 5 polystyrene and 5 poly(2-vinylpyridine) (P2VP) arms emanated from a poly(divinyl benzene) core and the chemical stabilization of the resulting supramolecular nano-objects in the bulk and in solution. To tune various morphologies from the same star copolymer, selective and nonselective solvent media were used. Thepyridine moieties, forming distinct P2VP nanodomains in the copolymer nanostructures, were selectively crosslinked using 1,4-dibromobutane under mild conditions to yield stabilized polymeric “hairy” nano-objects, dispersible in hot tetrahydrofuran. The morphology of the resulting nanostructures was studied using scanning electron microscopy and was found to be strongly dependent on various factors, such as the self-assembly/casting conditions, the total time of the crosslinking reaction, and the dispersion procedure. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 1636–1641, 2010     

Multisensitive polymers based on 2‐vinylpyridine and N‐isopropylacrylamide *

Poly(2‐vinylpyridine) (P2VP) containing functionalized end groups was synthesized using nitroxyl‐mediated radical polymerization with a hydroxy‐functionalized stable free radical. It was shown that P2VP could be synthesized with variable molar masses and low polydispersities. The transformation of the hydroxy groups to an acrylic ester led to the formation of macromonomers. A free‐radical copolymerization of these macromonomers with N‐isopropylacrylamide gave a graft copolymer with a poly(N‐ispopropylacrylamide) backbone and P2VP side chains. Polymers containing different amounts of the monomers were synthesized. It was possible to vary both the amount of P2VP side chains at a constant chain length of the macromonomer and the chain length at a nearly constant chain number. The behavior of the multifunctional macromolecules at different temperatures and pH values was investigated using dynamic light scattering and DSC. The macromolecules were found to retain the specific properties of the homopolymers. The hydrodynamic radii of the synthesized graft copolymers were both dependent on the temperature and pH value. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3797–3804, 2001     

Controlled Nanopores in Thin Films of Nonstoichiometrically Supramolecularly Assembled Graft Copolymers

Herein, nanometer‐scale morphologies of graft‐copolymer‐like supramolecular thin films, composed of sulfonic acid terminated polystyrene (SPS) and poly(2‐vinylpyridine) (P2VP), and their application to antireflection coatings were investigated. The intermolecular complexes of SPS and P2VP, formed through nonstoichiometric multiple hydrogen bonding between the sulfonic acid group of SPS and the nitrogen atom in pyridine unit of P2VP, occurring in film deposition allowed for the formation of spherical micelles (with SPS and P2VP as the corona and core, respectively) in the thin film. Interestingly, the domain size of the micelles was tunable from approximately 20 to 90 nm on average by controlling either the blend ratio of components or the concentration of polymer solution. Furthermore, nanoporous thin films could be easily prepared by removing the core of micelle‐based nanostructures by using a simple solvent etching process, leaving sulfonic acid groups on the surface of nanopores, which can be utilized as potential functional sites. Those resultant nanoporous thin films were conveniently employed as an antireflection layer on a glass substrate, giving a maximum 97.8 % transmittance in the visible wavelength range.     

Double‐hydrophilic block copolymer for encapsulation and two‐way pH change‐induced release of metalloporphyrins

A double hydrophilic block copolymer composed of poly(acrylic acid) (PAA) and poly(4‐vinyl pyridine) (P4VP) was obtained through hydrolysis of diblock copolymer of poly(tert‐butyl acrylate) (PtBA) and P4VP synthesized using atom transfer radical polymerization. Water‐soluble micelles with PAA core and P4VP corona were observed at low (acidic) pH, while micelles with P4VP core and PAA corona were formed at high (basic) pH. Two metalloporphyrins, zinc tetraphenylporphyrin (ZnTPP) and cobalt tetraphenylporphyrin (CoTPP), were used as model compounds to investigate the encapsulation of hydrophobic molecules by both types of micelles. UV–vis spectroscopic measurements indicate that micelles with P4VP core are able to entrap more ZnTPP and CoTPP as a result of the axial coordination between the transition metals and the pyridine groups. The study found that metalloporphyrins encapsulated by the micelles with PAA core could be released on pH increase, while those entrapped by the micelles with P4VP core could be released on pH decrease. This behavior originates from the two‐way pH change‐induced disruption of PAA‐b‐P4VP micelles. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 1734–1744, 2006     

Molecular‐level structures at poly(4‐vinyl pyridine)/acid interfaces probed by nonlinear vibrational spectroscopy

The molecular structures of the interfaces between a solid poly(4‐vinyl pyridine) (P4VP) surface and poly(acrylic acid) (PAA) as well as hydrochloric acid (HCl) solutions were probed using sum frequency generation (SFG) vibrational spectroscopy in situ in real time. Spectroscopic results clearly reveal that the PAA molecules are adsorbed onto the P4VP surface via hydrogen bonding at the P4VP/PAA solution interface while the P4VP surface is protonated at the P4VP/HCl solution interface. Consequently, the water molecules near the interfaces are strongly perturbed by these two interactions, exhibiting different orderings at the two interfaces. This work clearly demonstrates the power of studying the interfacial molecular‐level structures via nonlinear vibrational spectroscopy when molecular adsorption happens at the solid–liquid interface and paves a way for our future study on tracing the adsorption dynamics of polymer chains onto solid surfaces. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 848–852     

Preparation of polymeric vesicles through ultrasonic treatment of poly(styrene‐block‐2‐vinylpyridine) micelles under alkaline conditions

An approach for the preparation of block copolymer vesicles through ultrasonic treatment of polystyrene‐block‐poly(2‐vinyl pyridine) (PS‐b‐P2VP) micelles under alkaline conditions is reported. PS‐b‐P2VP block copolymers in toluene, a selective solvent for PS, form spherical micelles. If a small amount of NaOH solution is added to the micelles solution during ultrasonic treatment, organic‐inorganic Janus‐like particles composed of the PS‐b‐P2VP block copolymers and NaOH are generated. After removal of NaOH, block copolymer vesicles are obtained. A possible mechanism for the morphological transition from spherical micelles to vesicles or Janus‐like particles is discussed. If the block copolymer micelles contain inorganic precursors, such as FeCl₃, hybrid vesicles are formed, which may be useful as biological and chemical sensors or nanostructured templates. © 2014 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 953–959     

Synthesis of well‐defined pH‐responsive PPEGMEA‐g‐P2VP double hydrophilic graft copolymer via sequential SET‐LRP and ATRP

A series of well‐defined double hydrophilic graft copolymers containing poly(poly(ethylene glycol) methyl ether acrylate) (PPEGMEA) backbone and poly(2‐vinylpyridine) (P2VP) side chains were synthesized by successive single electron transfer living radical polymerization (SET‐LRP) and atom transfer radical polymerization (ATRP). The backbone was first prepared by SET‐LRP of poly(ethylene glycol) methyl ether acrylate (PEGMEA) macromonomer using CuBr/tris(2‐(dimethylamino)ethyl)amine as catalytic system. The obtained homopolymer then reacted with lithium diisopropylamide and 2‐chloropropionyl chloride at ?78 °C to afford PPEGMEA‐Cl macroinitiator. poly(poly(ethylene glycol) methyl ether acrylate)‐g‐poly(2‐vinylpyridine) double hydrophilic graft copolymers were finally synthesized by. ATRP of 2‐vinylpyridine initiated by PPEGMEA‐Cl macroinitiator at 25 °C using CuCl/hexamethyldiethylenetriamine as catalytic system via the grafting‐ from strategy. The molecular weights of both the backbone and the side chains were controllable and the molecular weight distributions kept relatively narrow (M_w/M_n ≤ 1.40). pH‐Responsive micellization behavior was investigated by ¹H NMR, dynamic light scattering, and transmission electron microscopy and this kind of double hydrophilic graft copolymer aggregated to form micelles with P2VP‐core while pH of the aqueous solution was above 5.0. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Supramolecular Copolymerization by Sequence Reorganization of a Supramolecular Homopolymer

The homopolymeric sequence formed by the head‐to‐head association of tetrakisporphyrin 1 is completely dissociated by the competitive association of the ditopic guest G2 , resulting in the supramolecular copolymer poly‐ 1 ? G2 with an alternatingly repeating host–guest sequence. The 1:1 stoichiometry of 1 and G2 is confirmed by a Job plot using UV/Vis titration and diffusion‐ordered NMR spectroscopy (DOSY). The solution viscometry for poly‐ 1 and poly‐ 1 ? G2 suggests that the supramolecular chain of poly‐ 1 behaves like a rod, whereas the supramolecular copolymer chain of poly‐ 1 ? G2 behaves like a swelled fat chain, which is entangled in the semi‐dilute regime. Atomic force microscopy shows that the supramolecular polymer poly‐ 1 ? G2 is highly oriented through the interdigitation of the long alkyl chains.     

Self‐organization and luminescent properties of nanostructured europium (III)–block copolymer complex thin films

We introduce a simple method to create nanosized, ordered, and highly luminescent thin film of Eu (III)–block copolymer complex. Micelles of polystyrene–block‐poly(4‐vinylpyridine) (PS‐b‐P4VP) in P4VP‐selective solvents (ethanol/N,N‐dimethylformamide (DMF) mixture) serve as nanoreactors for the synthesis of Eu(III)–block copolymer complex with the presence of 1,10‐phenanthroline (Phen) as cooperative ligand. The resulted quaternary complexes were characterized by FT‐IR spectra, ¹⁵N NMR spectra, and elemental analysis, indicative of a composition of Eu(III)–(PS‐b‐P4VP)–Phen–5DMF. Atomic force microscopy and transmission electron microscopy investigations reveal that the Eu(III)–(PS‐b‐P4VP)–Phen–5DMF complex can self‐organize into hexagonally ordered thin films when dip‐coated from the solution onto silicon or silica glass substrates. Such ordered thin films can emit red fluorescence of Eu³⁺ with strong intensity and long lifetime. This method can be easily extended to prepare other ordered luminescent rare earth–polymer complexes thin films. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2181–2189, 2005     

Supramolecular Micellization of Diblock Copolymer Mixtures Mediated by Hydrogen Bonding for the Observation of Separated Coil and Chain Aggregation in Common Solvents

This paper describes a new approach towards preparing self‐assembled hydrogen‐bonded complexes that have vesicle and patched spherical structures from two species of block copolymer in non‐selective solvents. The assembly of vesicles from the intermolecular complex formed after mixing polystyrene‐block‐poly(4‐vinyl phenol) (PS‐b‐PVPh) with poly(methyl methacrylate)‐block‐poly(4‐vinylpyridine) (PMMA‐b‐P4VP) in tetrahydrofuran (THF) is driven by strong hydrogen bonding between the complementary binding sites on the PVPh and P4VP blocks. In contrast, well‐defined patched spherical micelles form after blending PS‐b‐PVPh with PMMA‐b‐P4VP in N,N‐dimethylformamide (DMF): weaker hydrogen bonds form between the PVPh and P4VP blocks in DMF, relative to those in THF, which results in the formation of spherical micelles that have compartmentalized coronas that consist of PS and PMMA blocks.

     

Synthesis and properties of fluorine‐containing amphiphilic graft copolymer P(HFMA)‐g‐P(SPEG)

A series of amphiphilic graft copolymers P(HFMA)‐g‐P(SPEG) comprising poly(hexafluorobutyl methacrylate) (PHFMA) backbones and poly(ethylene glycol) (PEG) side chains were synthesized by copolymerization of HFMA and SPEG macromonomer with the p‐vinylbenzyl end group. The SPEG macromonomer was synthesized by reacting Methoxy poly(ethylene glycol) (MPEG) with p‐chloromethylstyrene in THF in the presence of NaH. The macromonomer and amphiphilic graft copolymer were characterized by FTIR, ¹H NMR, ¹⁹F NMR, and gel permeation chromatography (GPC). The critical micelle concentration (CMC) of the amphiphilic graft copolymer was measured by surface tension technique. The results showed that the CMC decreased with increasing HFMA contents in the graft copolymers. The interaction between P(HFMA)‐g‐P(SPEG) and bovine serum albumin (BSA) was studied by fluorescence spectroscopy, transmission electron microscopy (TEM), and photon correlation spectroscopy (PCS). The fluorescence spectrum showed that the fluorescence intensity of BSA increased with increasing content of HFMA in P(HFMA)‐g‐P(SPEG) and concentration of P(HFMA)‐g‐P(SPEG) in the P(HFMA)‐g‐P(SPEG)/BSA solution. TEM micrographs showed that P(HFMA)‐g‐P(SPEG) mainly formed core‐shell structure micelles. When BSA was added, the micelles changed from a core‐shell structure into a worm‐like, vesicle‐like and hollow‐like structure with different initial concentrations of the copolymer. The size distribution of the micelles increased proving that the copolymer micelles encapsulated the bovine serum albumin. © 2009 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 47: 4895–4907, 2009     

A successive route to amphiphilic graft copolymers with a hydrophilic poly(3‐hydroxypropyl methacrylate) backbone and hydrophobic polystyrene side chains

A successive method for preparing novel amphiphilic graft copolymers with a hydrophilic backbone and hydrophobic side chains was developed. An anionic copolymerization of two bifunctional monomers, namely, allyl methacrylate (AMA) and a small amount of glycidyl methacrylate (GMA), was carried out in tetrahydrofuran (THF) with 1,1‐diphenylhexyllithium (DPHL) as the initiator in the presence of LiCl ([LiCl]/[DPHL]₀ = 2), at −50 °C. The copolymer poly(AMA‐co‐GMA) thus obtained possessed a controlled molecular weight and a narrow molecular weight distribution (M_w /M_n = 1.08–1.17). Without termination and polymer separation, a coupling reaction between the epoxy groups of this copolymer and anionic living polystyrene [poly(St)] at −40 °C generated a graft copolymer with a poly(AMA‐co‐GMA) backbone and poly(St) side chains. This graft copolymer was free of its precursors, and its molecular weight as well as its composition could be well controlled. To the completed coupling reaction solution, a THF solution of 9‐borabicyclo[3.3.1]nonane was added, and this was followed by the addition of sodium hydroxide and hydrogen peroxide. This hydroboration changed the AMA units of the backbone to 3‐hydroxypropyl methacrylate, and an amphiphilic graft copolymer with a hydrophilic poly(3‐hydroxypropyl methacrylate) backbone and hydrophobic poly(St) side chains was obtained. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1195–1202, 2000     

Synthesis and character of novel polycarbonate for constructing biodegradable multi‐stimuli responsive delivery system

Here, we design a novel triple‐stimuli‐sensitive graft copolymer assembly which responds to the changes in temperature, reducing agent, and light. The graft copolymer consists of thermo‐responsive tetraethylene glycolyl poly(trimethylene carbonate) (P(MTC‐4EG)) as backbone and light‐sensitive poly(2‐nitrobenzyl methacrylate) (PNBM) as side chain linked by an intervening disulfide bond. In aqueous solution, the polymer can self‐assemble into micelle with thermo‐sensitive shell (P(MTC‐4EG)), light‐sensitive core (PNBM), and disulfide linker. The assemblies in response to stimuli were revealed by dynamic light scatting (DLS) and transmission electron microscopy (TEM). The drug release behaviors of Nile Red (NR)‐loaded carriers were also valued with stimuli from temperature, reducing agent, and light. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016 , 54, 3583–3592     

Structural isomer effects on the morphology of block copolymer/metal salts hybrids

The structural isomer effects on phase behavior of block copolymer/FeCl₃ hybrids were investigated by comparing structures of two series of blends based on polystyrene‐b‐poly(4‐vinylpyridine) (PS‐P4VP) and polystyrene‐b‐poly(2‐vinylpyridine) (PS‐P2VP), with the same molecular weight and the same composition. By conbining fourier transform infrared (FT‐IR) spectroscopy and differencial scaninng calorimetry, successful achievements of selective dispersion of FeCl₃ into poly(vinylpyridine) phase via coordination were verified. Complementary morphological observation by transmission electron microscopy and small‐angle X‐ray scattering (SAXS), it has been clarified that phase behavior for two isomer series is considerably different. That is, neat PS‐P4VP formed thicker cylindrical domains than that of neat PS‐P2VP due to much stronger Flory‐Huggins interaction parameter χ, χ_PS‐P4VP » χ_PS‐P2VP. As for PS‐P2VP/FeCl₃ hybrids, morphological transition can be taken place at the smaller amount of metal salt; furthermore, P2VP blend series form lamellar structures with evidently larger periodic length at the same amount of metal salt. This is probably caused by the event that excess metal salt also contributes to lamellar expansion by localizing at the center of P2VP lamellar phase. Moreover, the saturation limit of introduced metal salt in P2VP was smaller than that in P4VP due to the steric hindrance for a lone pair electrons on nitrogen atoms directed to the main chain of P2VP. These results can be explained by the structural isomer effects on the conformation of the P2VP chains at coordinated state with FeCl₃, that is, P2VP chains prefer to form the intramolecular coordination due to the short range interaction so as to make themselves stiffer, whereas P4VP chains tend to adopt the long range interaction including intra‐ and intermolecular coordinations. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2014 , 52, 377–386