Synthesis and photopolymerization of 1-propenyl glycidyl ether

The ambifunctional monomer, 1-propenyl glycidyl ether, was prepared from allyl glycidyl ether, by a ruthenium-catalyzed isomerization reaction in high yield. 1-Propenyl glycidyl ether undergoes facile photoinduced cationic polymerization to yield a crosslinked polymer. The structure of this polymer was studied using ¹H- and, ¹³C-NMR spectroscopies and employing well-characterized related polymers as models. The model polymers were prepared by the cationic polymerization of allyl glycidyl ether with BF₃OEt₂ followed by isomerization of the pendant allyl groups by a ruthenium catalyst. Subsequently, the resulting polyether-bearing pendant 1-propenyl ether groups was subjected to a diaryliodonium salt-photoinitiated polymerization. A comparison of the spectra of the polymers indicated the presence of cyclic acetal units in the polymer backbone. © 1994 John Wiley & Sons, Inc.     

Graft block copolymers of propargyl methacrylate and vinyl acetate via a combination of RAFT/MADIX and click chemistry: Reaction analysis

Propargyl methacrylate with its acetylene function protected with a silyl group is polymerized via the reversible addition fragmentation chain transfer (RAFT) process, using cyanoisopropyl dithiobenzoate (CPDB) as RAFT agent, and subsequently deprotected to afford a polymer backbone where each repeated unit is decorated with an acetylene functionality (1000 < M_n < 13,600 g mol⁻¹, 1.07 < PDI < 1.29). In parallel, an azide functionalized xanthate (ethoxythiocarbonylsulfanyl‐acetic acid 3‐azido‐propyl ester) was employed to prepare narrow polydisperse poly(vinyl acetate) (M_n = 850 g mol⁻¹, PDI = 1.20). The two polymers are conjugated by Huisgen 1,3‐dipolar cycloaddition to afford narrow polydisperse comb polymer (1.12 < PDI < 1.18, 3400 < M_n < 12,500 g mol⁻¹, based on linear polystyrene calibration, 4500 < M < 15,600 g mol⁻¹). The study places special emphasis on following the copper catalyzed 1,3‐dipolar cycloaddition via Fourier Transform Infrared Spectroscopy (FTIR) as well as via on‐line UV–Vis photospectrometry on several model compounds, i.e. the nonmonomer inserted azido‐xanthate RAFT/MADIX agent as well as a 2‐propargyl‐2‐bromopropionate and 3‐azidopropyl‐2‐bromopropionate model compounds. A suitable absorption band in the VIS at 666 nm (tentatively assigned to a charge transfer complex between copper(I) and the forming triazole moieties) is identified as a promising sensor for following the click reaction kinetics, thus allowing for the rapid assessment of reaction completion in an on‐line fashion. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 155–173, 2008     

Synthesis and characterization of NLO chromophores bearing poly(1,6-heptadiyne)s for electro-optic application

We utilized the metathesis reaction to synthesize a new type of multifunctional polymer that contains a conjugated backbone and a second-order NLO chromophore as a pendant group. The 1,6-heptadiyne derivatives bearing NLO chromophores were easily polymerized by using a metathesis catalyst to give corresponding polymers with large optical nonlinearities. Molecular structural characterizations for the resulting polymers were achieved by ¹H- and ¹³C-NMR, FTIR, and UV-visible spectroscopies. Soluble polymers were obtained up to 72 mol % of chromophore monomer portion in the copolymer. These amorphous polymers exhibited good film-forming abilities and thermal stability. The electro-optic coefficient, r₃₃, of the poled polymer films was in the range of 0.5–10.1 pm/V, and the nonresonant values of the third-order NLO coefficient, χ⁽³⁾ was found to be about 10⁻¹¹ esu. © 1996 John Wiley & Sons, Inc.     

An Amorphous n-Type Conjugated Polymer with an Ultra-Rigid Planar Backbone

High charge carrier mobility polymer semiconductors are always semi-crystalline. Amorphous conjugated polymers represent another kind of polymer semiconductors with different charge transporting mechanism. Here we report the first near-amorphous n-type conjugated polymer with decent electron mobility, which features a remarkably rigid, straight and planar polymer backbone. The molecular design strategy is to copolymerize two fused-ring building blocks which are both electron-accepting, centrosymmetrical and planar. The polymer is the alternating copolymer of double B←N bridged bipyridine (BNBP) unit and benzobisthiazole (BBTz) unit. It shows a decent electron mobility of 0.34 cm² V⁻¹ s⁻¹ in organic field-effect transistors. The excellent electron transporting property of the polymer is possibly due to the ultrahigh backbone stiffness, small π-π stacking distance, and high molecular weight.     

Ion transport mechanisms in salt-doped polymerized zwitterionic electrolytes

Polyzwitterions (polyZIs), macromolecules with repeating ampholytic monomers, are a novel class of materials with attractive properties for battery electrolytes. In this study, we probe the ion transport characteristics and underlying mechanisms in two salt-doped (Li⁺-TFSI⁻) polyZIs of similar composition with contrasting zwitterion (ZI) ionic organization: pendant monomers organized via backbone-anion-cation (B-ZI⁻-ZI⁺, Motif B) and backbone-cation-anion (B-ZI⁺-ZI⁻, Motif C). Within both Motifs B and C, the counterion of the pendant-end ZI moiety shows higher mobility. Similarly, when comparing Li⁺ or TFSI⁻ across motifs, it is seen that the respective pendant-end counterion possesses higher mobility than its backbone-adjacent counterpart. Furthermore, when comparing counterions to same-position ZI moieties, TFSI⁻ is seen to possess higher mobility than Li⁺ in each case, a result rationalized by invoking the lower interaction strength between the TFSI⁻ and ZI⁺. Analysis of ion-transport mechanisms demonstrate that the mobility of countercharges to the pendant-end ZI moiety correlates with the ion-association relaxation timescale, similar to ideas noted in polymerized ionic liquids in past studies. However, the mobility of countercharges to the backbone-adjacent ZI moiety is shown to be correlated with a cage relaxation time, which incorporates the combined effects of frustrated motion due to the presence of the polymer backbone and pendant-end ZI moiety and the higher mobility in a population of lightly ZI-coordinated ions. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 578–588     

Charge transport properties of triphenylamine‐pendant polypeptide

The structurally ordered polymer, triphenylamine‐pendant polypeptide (PATPA: poly[γ‐4‐(N,N‐diphenylamino‐phenyl)‐L ‐glutamine]), was prepared in order to obtain high hole mobility and high thermal stability. The hole mobility obtained for PATPA (ca. 10⁻⁵ cm²/Vsec) at room temperature is higher than that for poly(N‐vinylcarbazole) (PVK) (ca. 10⁻⁷ cm²/Vsec) or that of carbazole‐pendant polypeptide (PCLG) (ca. 10⁻⁸ cm²/Vsec). These results are supported by thermally stimulated current (TSC) measurements because the TSC can be correlated with the mobility. The glass‐transition temperature (T_g) of PATPA was estimated to be about 130° by differential scanning calorimetry (DSC). From these results, PATPA is an alternative candidate as a photoconductive polymer with high thermal stability and high hole mobility. The ordered structure along the main chain is thought to facilitate hole transport. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 362–368, 2000     

Bridging Small Molecules to Conjugated Polymers: Efficient Thermally Activated Delayed Fluorescence with a Methyl-Substituted Phenylene Linker

Based on a “TADF + Linker” strategy (TADF=thermally activated delayed fluorescence), demonstrated here is the successful construction of conjugated polymers that allow highly efficient delayed fluorescence. Small molecular TADF blocks are linked together using a methyl-substituted phenylene linker to form polymers. With the growing number of methyl groups on the phenylene, the energy level of the local excited triplet state (³LE_b) from the delocalized polymer backbone gradually increases, and finally surpasses the charge-transfer triplet state (³CT). As a result, the diminished delayed fluorescence can be recovered for the tetramethyl phenylene containing polymer, revealing a record-high external quantum efficiency (EQE) of 23.5 % (68.8 cd A⁻¹, 60.0 lm W⁻¹) and Commission Internationale de l′Eclairage (CIE) coordinates of (0.25, 0.52). Combined with an orange-red TADF emitter, a bright white electroluminescence is also obtained with a peak EQE of 20.9 % (61.1 cd A⁻¹, 56.4 lm W⁻¹) and CIE coordinates of (0.36, 0.51).     

Structure-property study of polyimides derived from PMDA and BPDA dianhydrides with structurally different diamines

A series of aromatic diamines were polymerized with two aromatic dianhydrides, pyromellitic dianhydride and 3,3^′,4,4^′-biphenyltetracarboxylic dianhydride, and the resulting poly(amic acid)s were thermally cyclodehydrated to aromatic polyimides. The polyimides were characterized by determining the glass transition temperatures (T_g), thermal stability, coefficients of thermal expansion, and wide-angle X-ray diffraction. Structure-property relationships are elucidated and discussed in terms of the structural fragments in the polymer chain. The PMDA-based polyimides generally revealed a higher T_g than the corresponding BPDA-based analogues. Generally, the dilution of the imide content by the insertion of oxyphenylene segments into the diamines significantly reduced the T_g. The introduction of m- or o-phenylene units into the polymer backbone usually resulted in a decrease in T_g. The attachment of pendant groups on the backbone may lead to decreased or increased T_gs, depending on the structure of pendant groups. As evidenced by X-ray diffraction, the polyimides derived from rigid, rod-like diamines or the diamines having two or three p-oxyphenylene showed a higher crystalline tendency. The presence of aliphatic pendant groups slightly reduced the thermal stability of the polyimides. The other structural changes did not show a dramatic influence on the thermal stability. Some polyimides obtained from p- or m-phenylenediamine had low thermal expansion coefficients below 2×10−5°C⁻¹.     

Charge carrier mobilities in liquid crystalline mesomorphic poly(DI-n-Alkylsilylene)s; influence of backbone conformation

The charge transport properties of a series of symmetrically substituted mesomorphic poly(di-n-alkylsilylene)s are studied using the pulse-radiolysis time resolved microwave conductivity (PR-TRMC) technique. The observed conductivities for these polymers could be correlated with different backbone conformations present both in the crystalline solid phase and in the liquid crystalline mesophase. The transition from the solid phase to the mesophase is accompanied by a disordering of the silicon backbone that results in a decrease of the conductivity of up to two orders of magnitude. The charge carrier mobilities found varied from 5×10⁻⁵ m² /Vs for the all-trans conformation in the solid phase to 6×10⁻⁷ m² /Vs for the disordered backbone conformation in the mesophase. The anisotropic radiation-induced conductivity observed for aligned poly(di-n-hexylsilylene) samples demonstrate that charge carrier migration takes place preferentially in the direction of the polymer backbone.     

Kinetic study of the crosslinking reaction of 1,2‐polybutadiene with dicumyl peroxide in the absence and presence of vinyl acetate

The crosslinking reaction of 1,2-polybutadiene (1,2-PB) with dicumyl peroxide (DCPO) in dioxane was kinetically studied by means of Fourier transform near-infrared spectroscopy (FTNIR). The crosslinking reaction was followed in situ by the monitoring of the disappearance of the pendant vinyl group of 1,2-PB with FTNIR. The initial disappearance rate (R₀) of the vinyl group was expressed by R₀ = k[DCPO]^0.8[vinyl group]^−0.2 (120 °C). The overall activation energy of the reaction was estimated to be 38.3 kcal/mol. The unusual rate equation was explained in terms of the polymerization of the pendant vinyl group as an allyl monomer involving degradative chain transfer to the monomer. The reaction mixture involved electron spin resonance (ESR)-observable polymer radicals, of which the concentration rapidly increased with time owing to a progress of crosslinking after an induction period of 200 min. The crosslinking reaction of 1,2-PB with DCPO was also examined in the presence of vinyl acetate (VAc), which was regarded as a copolymerization of the vinyl group with VAc. The vinyl group of 1,2-PB was found to show a reactivity much higher than 1-octene and 3-methyl-1-hexene as model compounds in the copolymerization with VAc. This unexpectedly high reactivity of the vinyl group suggested that an intramolecular polymerization process proceeds between the pendant vinyl groups located on the same polymer chain, possibly leading to the formation of block-like polymer. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4437–4447, 2004     

An n-Type Polythiophene Derivative with Excellent Thermoelectric Performance

Typical n-type conjugated polymers are based on fused-ring electron-accepting building blocks. Herein, we report a non-fused-ring strategy to design n-type conjugated polymers, i.e. introducing electron-withdrawing imide or cyano groups to each thiophene unit of a non-fused-ring polythiophene backbone. The resulting polymer, n-PT1 , shows low LUMO/HOMO energy levels of −3.91 eV/−6.22 eV, high electron mobility of 0.39 cm² V⁻¹ s⁻¹ and high crystallinity in thin film. After n-doping, n-PT1 exhibits excellent thermoelectric performance with an electrical conductivity of 61.2 S cm⁻¹ and a power factor (PF) of 141.7 μW m⁻¹ K⁻². This PF is the highest value reported so far for n-type conjugated polymers and this is the first time for polythiophene derivatives to be used in n-type organic thermoelectrics. The excellent thermoelectric performance of n-PT1 is due to its superior tolerance to doping. This work indicates that polythiophene derivatives without fused rings are low-cost and high-performance n-type conjugated polymers.     

Polyfluorene Polyelectrolyte Nanoparticles: Synthesis of Innovative Stabilizers for Heterophase Polymerization

Polyfluorene‐bearing bromohexyl side chains are quaternized by 1‐vinylimidazole in order to attach dialkylimidazolium bromide ionic liquid (IL) species along the conjugated backbone. Subsequently, polyfluorene polyelectrolyte nanoparticles (NPs) of 40 nm in average size are created via radical cross‐linking of the pendant vinylimidazolium groups. Anion exchange from Br⁻ to BF₄⁻, PF₆⁻, and bis(trifluoromethylsulfonyl)imide anion (TFSI⁻) renders NPs adjustable dispersability in various organic solvents. The hydrophobic‐conjugated backbone and the hydrophilic dialkylimidazolium bromide IL moieties depict an amphiphilic profile, which allows the NPs to be deployed as conductive stabilizer in the emulsion polymerization of styrene. The resultant latexes are fluorescent, tunable in size and can be transferred to organic solvents without forfeiting their colloidal stability.

     

Facile Fabrication of Bio- and Dual-Functional Poly(2-oxazoline) Bottle-Brush Brush Surfaces

Poly(2-oxazoline)s (POx) bottle-brush brushes have excellent biocompatible and lubricious properties, which are promising for the functionalization of surfaces for biomedical devices. Herein, a facile synthesis of POx is reported which is based bottle-brush brushes (BBBs) on solid substrates. Initially, backbone brushes of poly(2-isopropenyl-2-oxazoline) (PIPOx) were fabricated via surface initiated Cu⁰ plate-mediated controlled radical polymerization (SI-Cu⁰CRP). Poly(2-methyl-2-oxazoline) (PMeOx) side chains were subsequently grafted from the PIPOx backbone via living cationic ring opening polymerization (LCROP), which result in ≈100 % increase in brush thickness (from 58 to 110 nm). The resultant BBBs shows tunable thickness up to 300 nm and high grafting density (σ) with 0.42 chains nm⁻². The synthetic procedure of POx BBBs can be further simplified by using SI-Cu⁰CRP with POx molecular brush as macromonomer (M_n=536 g mol⁻¹, PDI=1.10), which results in BBBs surface up to 60 nm with well-defined molecular structure. Both procedures are significantly superior to the state-of-art approaches for the synthesis of POx BBBs, which are promising to design bio-functional surfaces.     

Cyclopolymerization of 3-phenyl[5]ferrocenophane-1,5-dimethylene: Synthesis and electronic properties of a polyferrocenophane

Radical cyclopolymerization of 3-phenyl[5]ferrocenophane-1,5-dimethylene ( 2 ) and copolymerization with styrene gave polymers ( 3 and 4 ) with [3]ferrocenophane moieties pendant to the backbone. Cyclic voltammetry (CV) on polymer 3 in CH₂Cl₂ showed two oxidation waves at −0.13 and +0.05 V (versus ferrocene/ferrocenium) and CV on copolymer 4 showed one oxidation potential at −0.03 V. CV on 3 in dimethylacetamide showed only one oxidation potential at −0.10 V. Near-IR spectroscopy of partially oxidized 3 showed a broad intervalence band at ca. 2000 nm, indicative of low-energy barriers to electron hopping. Conductivity measurements on 3 and poly(vinylferrocene) (PVFc) oxidatively doped with iodine vapors under an argon atmosphere showed a maximum conductivity ca. 5 × 10⁻⁵ S/cm before the samples cracked, while 4 exhibited a maximum conductivity of 1.6 × 10⁻⁶ S/cm. On iodine doping under ambient conditions, polymers 3 , 4 , and PVFc showed maximum conductivities of 7.6 × 10⁻⁴, 9.5 × 10⁻⁵, and 5.5 × 10⁻⁵ S/cm, respectively. Conductivity measurement were also performed on samples of 3 ⁺BF₄⁻ with oxidation levels ranging from 8 to 56%. Conductivities of these samples ranged from ca. 10⁻¹⁰ to 10⁻⁹ S/cm under vacuum and ca. 10⁻⁶ S/cm under ambient conditions, indicating that atmospheric moisture has a strong effect on the conductivity. © 1997 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 35 : 3365–3376, 1997     

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.     

Novel amine-containing biodegradable polyester via copolymerization of aspartic anhydride and 1,4-cyclohexanedimethanol

A novel biodegradable polyester having pendant amine functional groups was snythesized from N-(benzyloxycarbonyl)-L -aspartic anhydride ( 2 ) and 1,4-cyclohexanedimethanol ( 3 ) by polycondensation reaction using p-toluenesulfonic acid as a catalyst. The synthesized polymer 4 shows the characteristic ester carbonyl absorption peak at 1732 cm⁻¹ in the IR spectrum, and the NMR spectra were consistent with the IR data. Also, the elemental analysis showed that the experimental and calculated values were very close to each other. The weight-average molecular weight of the polymers ranged from 1140 to 5050 and increased with increasing reaction time. This new polymer would have the potential of a drug delivery biomaterial.     

Molecular engineering of pyroelectric polysiloxane Langmuir-Blodgett superlattices: synthesis,film preparation and pyroelectric properties

A wide range of linear and cyclic polysiloxanes substituted with side chains containing carboxylic acid groups have been synthesized and characterized in terms of their Langmuir/Langmuir-Blodgett (LB) film properties and their pyroelectric activity. The effects on these properties of varying the degree of side-group substitution, the length of aliphatic side groups, the incorporation of polar aromatic side groups and the deposition conditions utilized during the preparation of multilayer assemblies have been investigated. These materials form stable Langmuir layers at the air-water interface which can be transferred onto substrates such as glass and aluminium-coated glass. The alternate layer LB deposition technique, in which each polysiloxane layer is co-deposited in an alternating stacking sequence with monolayers of a monomeric aliphatic amine compound, has been used to fabricate macroscopically polar films which display a temperature-dependent electric polarization, the ‘pyroelectric effect’. Data are presented here for both linear and cyclic substituted polymer backbones showing that both systems provide useful insight into the pyroelectric behaviour of organic materials. Trends in the relationships between the pyroelectric activity and (1) the chemical structure of the materials and (2) the structure of the acid/amine superlattice have been identified and indicate that the optimum pyroelectric coefficient is observed for a linear copolysiloxane compound substituted with a polar aromatic pendant side group. Indeed, the pyroelectric coefficient measured for this material is ∼10μCm⁻² K⁻¹ which is currently the highest value reported for an LB assembly to our knowledge.     

Synthesis of thermally degradable epoxy adhesives

We have developed a new strategy for the synthesis of epoxide‐containing polymers where the pendant reactive groups are connected to the main backbone via thermally labile oxonorbornene groups. The polymers were synthesized by radical 1,4‐polymerization of the appropriate bicyclic diene monomer. The produced polymers can be crosslinked in the presence of a diamine and de‐crosslinked by thermal treatment at 160 °C, which induces retro‐Diels–Alder reaction and cleaves pendant groups from the polymer backbone, as confirmed by differential scanning calorimetry. The potential for the utilization of this polymer as a thermally removable adhesive was demonstrated by a simple adhesion test. This method provides access to thermally cleavable epoxy networks that can be quickly and irreversibly disintegrated into nonvolatile components upon heating to a specified temperature. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 4992–4997     

Synthesis of a conjugated polymer for sensing ferric/ferrous cations based on dual responses

A conjugated polymer (PPETE-RB) with poly[p-(phenylene ethynylene)-alt-(thienylene-ethynylene)] (PPETE) as the backbone with pendant rhodamine B (RB) groups in the close-ring spirolactam form was synthesized. With long spacer between backbone and pedant groups as well as long solubilizing side chains, the polymer possesses good solubility in most organic solvents and relatively large molecular weight. The fluorescence of the conjugated polymer in THF exhibited selective dual responses upon adding Fe³⁺/Fe²⁺ but negligible response upon other cations. The emission around 481 nm (excited at 360 nm) decreased and that around 571 nm (excited at 520 nm) emerged and increased when increasing the concentration of iron ions. The responses to Fe³⁺ and Fe²⁺ are very similar. The limits of detection were found to fall in between 6 μM and 8 μM. The mechanism study showed that the quenching around 481 nm was due to the inner filter effect (IFE) between the Fe³⁺/Fe²⁺ and PPETE-RB; while that enhancement around 571 nm could be attributed to the formation of fluorescent ring-open structure from nonfluorescent spirolactam of pedant RB group upon Fe³⁺/Fe²⁺. Such dual and opposite responses provided more reliable information than single response for sensing applications.     

Novel fluorescent amphiphilic poly(allylamine) and their supramacromolecular self‐assemblies in aqueous media

Fluorescent amphiphilic polymers were produced by grafting different types and levels of hydrophobic pendant groups with intrinsic fluorescent properties (fluorenylmethoxy carbonyl (Fmoc), dimethylamino‐1‐naphthalenesulfonyl (Dansyl), and naphthalene (Naphth) to a water soluble homopolymer backbone, polyallylamine (PAA). Non‐fluorescent hydrophobic pendant group (cholesteryl moieties) were also grafted onto PAA. The polymers were characterized with elemental analysis, NMR and FTIR spectroscopy. All polymers formed self‐assemblies by probe sonication in water with sizes ranging from 120 to 199 nm and TEM images showed the presence of spherical particles. The critical aggregation concentration (CAC) varied from 0.093 to 1.5 mg ml^?1 depending on the type of hydrophobic pendant groups. The Cholesteryl and Dansyl polymers showed the presence of one CAC while the Fmoc and Naphth grafted polymers revealed the presence of two CACs. The first CAC observed was possibly due to intermolecular aggregation while the second CAC at the higher polymer concentration was the result of excimer formation revealed by their fluorescent spectra. We reasoned that Naphth and Fmoc aromatic pendant groups possess a flat stereochemistry, thus allowing π–π stacking at higher concentrations. The presence of the N‐dimethylamino group in the Dansyl moiety gives rise to a 3D structure, thus hindering any stacking. The understanding of the supramolecular assemblies formed by these fluorescent amphiphilic polymers will aid in the engineering of advanced materials with superior functionality for biomedical applications. Copyright © 2011 John Wiley & Sons, Ltd.