Higher Generation Dendrons Research Articles

Blood Compatibility of Amphiphilic Phosphorous Dendrons-Prospective Drug Nanocarriers.

Dendrons are branched synthetic polymers suitable for preparation of nanosized drug delivery systems. Their interactions with biological systems are mainly predetermined by their chemical structure, terminal groups, surface charge, and the number of branched layers (generation). Any new compound intended to be used, alone or in combination, for medical purposes in humans must be compatible with blood. This study combined results from in vitro experiments on human blood and from laboratory experiments designed to assess the effect of amphiphilic phosphorous dendrons on blood components and model membranes, and to examine the presence and nature of interactions leading to a potential safety concern. The changes in hematological and coagulation parameters upon the addition of dendrons in the concentration range of 2–10 µM were monitored. We found that only the combination of higher concentration and higher generation of the dendron affected the selected clinically relevant parameters: it significantly decreased platelet count and plateletcrit, shortened thrombin time, and increased activated partial thromboplastin time. At the same time, occasional small-sized platelet clumps in blood films under the light microscope were observed. We further investigated aggregation propensity of the positively charged dendrons in model conditions using zwitterionic and negatively charged liposomes. The observed changes in size and zeta potential indicated the electrostatic nature of the interaction. Overall, we proved that the low-generation amphiphilic phosphorous dendrons were compatible with blood within the studied concentration range. However, interactions between high-generation dendrons at bulk concentrations above 10 µM and platelets and/or clotting factors cannot be excluded.

Dendronized Arm Snowflake Polymer as a Highly Branched Scaffold for Cellular Imaging and Delivery.

Incorporation of branched structures is a major pathway to build macromolecules with desired three-dimensional (3D) structures, which are of high importance in the rational design of functional polymeric scaffolds. Dendrimers and hyperbranched polymers have been extensively studied for this purpose, but proper gain-of-function for these structures usually requires large enough molecular weights and a highly branched interior so that a spherical 3D core-shell architecture can be obtained, yet it is generally challenging to achieve precise control over the structure, high molecular weight, and high degree of branching (DoB) simultaneously. In this article, we present a set of snowflake-shaped star polymers with functional cores and dendronized arms, which ensure a high DoB and an overall globular conformation, thus facilitating the introduction of functional moieties onto the easily achieved scaffold without the need for high-generation dendrons. Using a polyglycerol dendron (PGD) as a proof of concept, we propose that this dendronized arm snowflake polymer (DASP) structure can serve as a better performing alternative to high-generation PGDs. DASPs with molecular weights of 750, 1220, 2120, and 3740 kDa were prepared with >85% yields in all cases, and we show that these DASPs have high encapsulating efficiency of Nile Red due to their high DoB and high biocompatibility due to their hydroxyl-rich nature after ketal removal, as well as high cell permeability that is molecular-weight-dependent. Introduced fluorophores such as fluorescein and difluoroboron 1,3-diphenylaminophenyl β-diketonate with suitable excitation wavelengths may turn the DASPs into stable, endosome-staining fluorophores with ultra-large Stokes shifts, narrowed emission bands, and suitability for long-term cellular tracing. Moreover, the scaffold can encapsulate antibiotic molecules and deliver them into phagolysosomes for efficient elimination of intracellular Staphylococcus aureus, which is insensitive toward many antibiotics but is a key target for the clinical success of methicillin-resistant Staphylococcus aureus infection treatment. Elimination of Staphylococcus aureus could be improved to >99.9% for chloramphenicol at 32 μg/mL with 450 μg/mL DASP.

Direct Measure of the Local Concentration of Pyrenyl Groups in Pyrene-Labeled Dendrons Derived from the Rate of Fluorescence Collisional Quenching

The model-free analysis (MFA) was applied to measure the average rate constant (<k>) for pyrene excimer formation (PEF) in a series of pyrene-labeled dendrons referred to as Pyx-G(N), where x (= 2N) is the number of pyrenyl labels born by a dendron of generation N ranging from 1 to 6. <k> was measured in four different solvents, namely tetrahydrofuran (THF), toluene, N,N-dimethylformamide (DMF), and dimethylsulfoxide (DMSO). <k> was found to increase linearly with increasing local pyrene concentration ([Py]loc), where [Py]loc had been determined mathematically for the Pyx-G(N) dendrons. The slope of each straight line changed with the nature of the solvent and represented kdiff, the bimolecular rate constant for PEF. kdiff depended on the solvent viscosity (η) and the probability (p) for PEF upon encounter between an excited and a ground-state pyrene. In a same solvent, kdiff for the Pyx-G(N) dendrons was about 360 ± 30 times smaller than kdiff obtained for ethyl 4-(1-pyrene)butyrate (PyBE), a pyrene model compound similar to the pyrene derivative used to label the dendrons. The massive decrease in kdiff observed for the Pyx-G(N) samples reflected the massive loss in mobility experienced by the pyrenyl labels after being covalently attached onto a macromolecule compared to freely diffusing PyBE. Interestingly, the kdiff values obtained for the Pyx-G(N) dendrons and the PyBE model compound followed similar trends as a function of solvent, indicating that the difference in behavior between the kdiff values obtained in different solvents were merely due to the changes in the η and p values between the solvents. Normalizing the <k> values obtained with the Pyx-G(N) dendrons by the kdiff values obtained for PyBE in the same solvents accounted for changes in η and p, resulting in a master curve upon plotting <k>/(fdiff × kdiff) as a function of [Py]loc, where fdiff was introduced to account for some pyrene aggregation in the higher generation dendron (Py64-G(6)). This result demonstrates that <k> represents a direct measure of [Py]loc in pyrene-labeled macromolecules.

Mechanisms underlying interactions between PAMAM dendron-grafted surfaces with DPPC membranes.

Biofouling is a pervasive problem which demands the creation of smart, antifouling surfaces. Towards this end, we examine the interactions between a dipalmitoylphosphatidylcholine (DPPC) lipid bilayer and a polyamidoamine (PAMAM) dendron-grafted surface. In addition, we investigate the impact of dendron generation on the system behavior. To resolve the multiscale dynamical processes occurring over a large spatial scale, we employ Molecular Dynamics simulations with a coarse-grained implicit solvent force field. Our results demonstrate the transient and equilibrium system dynamics to be determined by the PAMAM dendron generation along with the underlying mechanisms. Higher generation dendrons are observed to favor penetration of the DPPC molecules into the dendron branches, thereby enabling sustained interactions between the membrane and the dendron-grafted surface. Under equilibrium, the membrane adopts a bowl-shaped morphology whose dimensions are determined by the dendron generation and density of interactions. The results from our study can be used to guide the design of novel surfaces with selective antifouling properties which can prevent the adsorption of microorganisms onto lipid membranes.

Designer Peptide Dendrons and Dendrimers Based Soft Materials Through Self‐Assembly

AbstractA series of new aspartic and glutamic acid based peptide dendrons and dendrimers were designed and synthesized. The supramolecular assembly of these novel molecules were studied by scanning electron microscopy (SEM), atomic force microscopy (AFM), and attenuated total reflectance Fourier transform infrared (ATR‐FTIR) spectroscopy. The dendrons and dendrimers formed gel in aqueous or in organic phase with excellent storage modulus as measured by rheometry. Glutamic acid‐based higher generation dendrons and dendrimers showed a minimum gelation concentration as low as 1 wt/v (%) in CHCl3. Interestingly, the higher generation dendrimers 5 d, 6 d, and 7 d gelated even polar solvent DMSO. The lipidated peptide dendrons showed thermotropic liquid crystalline behavior with the formation of columnar and smectic phase as confirmed by differential scanning calorimetry (DSC) and polarization optical microscopy (POM). These lipidated peptides exhibited well‐ordered specific modes of self‐assembly and hence could be exploited for several applications such as drug delivery vehicles and in tissue engineering.

ChemInform Abstract: Synthesis of Optically Active, X‐Shaped, Conjugated Compounds and Dendrimers Based on Planar Chiral [2.2]Paracyclophane, Leading to Highly Emissive Circularly Polarized Luminescence.

Optically active, Frechet-type dendrimers containing an emissive X-shaped π-electron system as the core unit were synthesized. Gram-scale optical resolution and transformations of 4,7,12,15-tetrasubstituted [2.2]paracyclophanes were also carried out. The high-generation dendrons effectively absorbed UV light and transferred energy to the core, resulting in high photoluminescence (PL) from the core. In addition, the dendrons sufficiently isolated the emissive X-shaped conjugated core and bright emission was observed from both thin films and solutions. Intense circularly polarized luminescence (CPL) was observed from the thin film. The dendrimer films exhibited excellent optical properties, such as large molar extinction coefficients, high fluorescence quantum efficiencies, intense PL and CPL, and large CPL dissymmetry factors.

Synthesis of Optically Active, X-Shaped, Conjugated Compounds and Dendrimers Based on Planar Chiral [2.2]Paracyclophane, Leading to Highly Emissive Circularly Polarized Luminescence.

Optically active, Fréchet-type dendrimers containing an emissive X-shaped π-electron system as the core unit were synthesized. Gram-scale optical resolution and transformations of 4,7,12,15-tetrasubstituted [2.2]paracyclophanes were also carried out. The high-generation dendrons effectively absorbed UV light and transferred energy to the core, resulting in high photoluminescence (PL) from the core. In addition, the dendrons sufficiently isolated the emissive X-shaped conjugated core and bright emission was observed from both thin films and solutions. Intense circularly polarized luminescence (CPL) was observed from the thin film. The dendrimer films exhibited excellent optical properties, such as large molar extinction coefficients, high fluorescence quantum efficiencies, intense PL and CPL, and large CPL dissymmetry factors.

Synthesis and characterization of solution-processible anthracene- based deep-blue fluorescent dendrimers

Anthracene has been intensively studied as an attractive building block for deep-blue fluorescent emitters due to its wide band gap and high photoluminescence quantum yield (PLQY) in dilute solution. In solid state, however, these anthracene derivatives seem to aggregate or crystallize, leading to the quenched fluorescence, red-shifted emission and poor device lifetime. Therefore, there are few reports about anthracene-based deep-blue emitters suitable for solution-processed undoped devices. To this end, herein we have designed and synthesized a series of solution-processible deep-blue fluorescent dendrimers (Ent1, Ent2 and Ent3) by using 9,10-diphenylanthracene (DPA) as the central core and 1st to 3rd generation oligocarbazole as the peripheral dendron. Unlike DPA that tends to crystallize in the solid state, Ent1~Ent3 are thermally stable, showing very high glass transition temperatures up to 194−371oC without any related signals from the crystallization or melting processes. As determined by atomic force microscopy (AFM), in addition, both the pristine and annealed films of Ent1~Ent3 have a fairly smooth surface with a root-mean-square roughness of 0.33-0.47 nm, indicative of their morphology stability. Meanwhile, the introduction of dendrons can effectively suppress the intermolecular interactions and thus enhance the film PLQY from 46% of Ent1 to 52% of Ent2 and 67% of Ent3. Correspondingly, as a result of the much richer electron-cloud density from the higher generation dendron, the highest occupied molecular orbital (HOMO) energy level is increased from −5.51 eV of Ent1 to −5.37 eV of Ent2 and −5.34 eV of Ent3, which is beneficial for the hole injection. Solution-processed undoped organic light-emitting diodes (OLEDs) are subsequently fabricated with a configuration of ITO\PEDOT:PSS(40 nm)\Ent1~Ent3(40 nm)\TPBI(55 nm)\LiF(1 nm)\Al(100 nm). All the dendrimers display a bright deep-blue emission with Commission International De L’Eclairge (CIE) coordinates of (0.16, 0.11), (0.16, 0.10) and (0.16, 0.09) for Ent1, Ent2 and Ent3, respectively. Noticeably, the turn-on voltage is firstly down from 4.2 V of Ent1 to 3.8 V of Ent2, and then up to 4.8 V of Ent3. This observation means that, albeit the facilitated hole injection, the electron injection would become more difficult in Ent3 owing to its shallow lowest unoccupied molecular orbital (LUMO) level. Therefore, among Ent1~Ent3, more balanced charge injection/transporting and efficient recombination could be expected for the 2nd generation dendrimer Ent2. Consequently, Ent2 obtains the best device performance, revealing a maximum luminous efficiency of 2.63 cd/A, a maximum power efficiency of 2.07 lm/W and a maximum external quantum efficiency of 2.48%. Our results demonstrate a promising approach to the development of solution processible deep-blue fluorescent emitters for undoped OLEDs applications.

Heparin versus DNA: Chiral Preferences in Polyanion Binding to Self-Assembled Multivalent (SAMul) Nanostructures.

This communication presents simple cationic self-assembling multivalent (SAMul) first generation dendrons based on L or D lysine, which form identical nanoscale assemblies in terms of dimensions and charge densities but toward which DNA and heparin exhibit different chiral binding preferences. However, higher generation dendrons with larger hydrophilic head groups are bound identically by these polyanions, irrespective of chirality. We propose that well-organized chiral ligands on the surface of self-assembled nanostructures can exhibit enantioselective polyanion binding. This demonstrates that small structural changes can be amplified by self-assembly and impact on nanoscale binding.

The influence of pentafluorophenyl groups on the nonlinear optical (NLO) performance of high generation dendrons and dendrimers.

With the aim to make the influence of pentafluorophenyl groups in the periphery of high generation dendrons and dendrimers on their NLO performance clearly, some NLO dendrons and dendrimers with different chromophore moieties or different end-capped groups were carefully designed and investigated in detail. The results demonstrated that some strong Ar-ArF interactions between the pentafluorophenyl groups in the periphery and the normal phenyl rings of the donors, could influence the topological structures of dendrons or dendrimers, and then affect their NLO performance. Furthermore, the optical transparency and the stability of the dendrons and dendrimers with pentafluorophenyl groups as end-capped moieties were all improved, in comparison with normal dendrons and dendrimers containing phenyl ones as the end-capped groups.

Novel dendritic-poly(urethane-urea) hybrid thin films from hydrogen bond rich dendrons

Hydrogen bond rich segmented poly(urethane-urea) was synthesized from methylene diphenylisocyanate (MDI) and three generations of polyurea-malonamide dendrons as hard segment and polycaprolactone diol as soft segment for thin film applications. The prepared polymers were characterized using spectroscopic, microscopic and thermal analyses. The formation of urethane linkage during the prepolymer reaction and the urea linkage between prepolymer and the dendrons is confirmed by Fourier transform infrared (FTIR) spectroscopy and 1H nuclear magnetic resonance (NMR) spectroscopy. FTIR shows the presence of hydrogen bonding of –NH groups with both urethane carbonyl group from hard segment and the ether group from the soft segment. However, the phase mixing of hard and soft segments decreases with the higher generation dendrons, as evidenced from FTIR. This observation was confirmed by phase images of the atomic force microscopy (AFM). The coating when applied to clean steel substrates via dip coating reveals uniform, dense and essentially defect free morphology. The work demonstrates that the mechanical properties of the hybrid thin films are dependent on the generation of the dendrons and provides a platform for surface engineering with tunable elastic modulus.

Solution Properties of Tadpole-type Cationic Amphiphilic Dendrimers Consisting of an Alkyl Chain, a Quaternary Ammonium, and a Poly(amidoamine) Dendron

Tadpole-type amphiphilic dendrimers consisting of an alkyl chain, a quaternary ammonium bromide (qb) and a poly(amidoamine) dendron (den) (CnqbdenGm, where n represents an alkyl chain with a length of 10,14, or 18 carbons; m is the generation number G of dendron taking the value -0.5, 0.5, or 1.5) were synthesized using N, N-dimethylethylenediamine as a central scaffold. Electrical conductivity, surface tension, pyrene fluorescence, and dynamic light scattering measurements were used to characterize the properties of the dendrimers. In addition, the effect of the alkyl chain length and the generation number of a dendron on these properties was evaluated through a comparison with those of the corresponding previously reported amphiphilic dendrimers with lactobionamide sugar terminal groups (CnqbdenGmLac) and conventional cationic monomeric surfactants (CnTAB). Both critical micelle concentration (cmc) and surface tension (except for C18 series) were lower than those of CnqbdenGmLac and CnTAB with the same alkyl chain length, indicating that the synthesized amphiphilic dendrimers have an excellent micelle-forming ability in solution and high adsorption ability at the air/water interface, in spite of the large bulky dendron structure. When the alkyl chain length and the generation number of the amphiphilic dendrimers were increased, the surface tension became high because of the curved long alkyl chain and the bulky structure of dendron. Further, CnqbdenGm formed micelles with a small size in solution, and the micelles of CnqbdenG(-0.5) had almost a constant size despite the changes in the concentration, while those of CnqbdenG0.5 and CnqbdenG1.5 became smaller with increasing concentration. The difference in the behavior results from the difference in the number of amide groups in the low- and high-generation dendrons.

Synthesis and Characterization of Novel Pyrene-Dendronized Porphyrins Exhibiting Efficient Fluorescence Resonance Energy Transfer: Optical and Photophysical Properties

A novel series of pyrene dendronized porphyrins bearing two and four pyrenyl groups (Py(2)-TMEG1 and Py(4)-TMEG2) were successfully synthesized. First and second generation Fréchet type dendrons (Py(2)-G1OH and Py(4)-G2OH) were prepared from 1-pyrenylbutanol and 3,5-dihydroxybenzyl alcohol. These compounds were further linked to a trimesitylphenylporphyrin containing a butyric acid spacer via an esterification reaction to obtain the desired products. Dendrons and dendronized porphyrins were fully characterized by FTIR and (1)H NMR spectroscopy and their molecular weights were determined by matrix-assisted laser desorption ionization time of flight mass spectrometry. Their optical and photophysical properties were studied by absorption and fluorescence spectroscopies. The formation of dynamic excimers was detected in the pyrene-labeled dendrons, with more excimer being produced in the higher generation dendron. The fluorescence spectra of the pyrene dendronized porphyrins exhibited a significant decrease in the amount of pyrene monomer and excimer emission, jointly with the appearance of a new emission band at 661 nm characteristic of porphyrin emission, an indication that fluorescence resonance energy transfer (FRET) occurred from one of the excited pyrene species to the porphyrin. The FRET efficiency was found to be almost quantitative ranging between 97% and 99% depending on the construct. Model Free analysis of the fluorescence decays acquired with the pyrene monomer, excimer, and porphyrin core established that only residual pyrene excimer formation in the dendrons could occur before FRET from the excited pyrene monomer to the ground-state porphyrin core.

Dendron‐Containing Tetraphenylethylene Compounds: Dependence of Fluorescence and Photocyclization Reactivity on the Dendron Generation

The synthesis and characterization of four dendron-containing tetraphenylethylenes (TPEs), 1(1)-1(4), were synthesized, along with a TPE compound that contained four OCH(2) Ph groups (referred to as 1(0)) for comparison. Photophysical studies revealed that the TPE core became emissive after linking dendrons onto its periphery. Moreover, the fluorescence intensity was significantly enhanced when high-generation dendrons were linked onto the TPE core; the fluorescence intensity increased in the following order: 1(1)<1(2)<1(3)<1(4). This phenomenon was tentatively attributed to an enhancement in the energy barrier for internal rotation and torsion of the TPE core to which four dendrons were connected. In addition, the photocyclization of the TPE core into the respective 9,10-diphenylphenanthrene was facilitated when high-generation dendrons were linked to the TPE core. Again, the photocycliztion reactivity increased in the following order: 1(1)<1(2)<1(3)<1(4). We found that the fluorescence and photocyclization reactivity of TPE could be modulated by covalent interactions with dendrons, and such modulation was strongly dependent on the dendron-generation.

Using a breath-figure method to self-organize honeycomb-like polymeric films from dendritic side-chain polymers

In this study, we investigated various generations of waxy dendrons, dendritic side-chain polymers (varying the structure and polarity of the polymer backbone), and physical blends of dendrons with polymers for their ability to form honeycomb-like structures. Each waxy dendron comprises a focal part (possessing many hydrogen bonding sites) and a peripheral part (rich in units that undergo van der Waals interactions). Using a breath-figure process, we readily incorporated high-generation dendrons within polymer matrixes to form porous surfaces. When the high-generation waxy dendrons were grafted onto amino group – functionalized polystyrene or copolymerized with diisocyanates to form polyurethanes, the multiple long alkyl chains behaved as bristles of hydrophobic brooms, due to the presence of strong van der Waals forces. The formation of honeycomb-like patterns in the polymer films resulted from strong hydrogen bonding of the polymers to water droplets on the surfaces of substrates, with subsequent self-organization and phase separation.

Hydrophobically Modified Dendrons: Developing Structure−Activity Relationships for DNA Binding and Gene Transfection

This paper develops a structure-activity relationship understanding of the way in which surfactant-like dendrons with hydrophilic spermine surface groups and a variety of lipophilic units at their focal points can self-assemble and subsequently bind to DNA with high affinity. The choice of functional group at the focal point of the dendron and the high tunability of the molecular structure have a very significant impact on DNA binding. Mesoscale modeling of the mode of dendron self-assembly provides a direct insight into how the mode of self-assembly exerts its effect on the DNA binding process. In particular, the hydrophobic unit controls the number of dendrons in the self-assembled micellar structures, and hence their diameters and surface charge density. The DNA binding affinity correlates with the surface charge density of the dendron aggregates. Furthermore, these structure-activity effects can also be extended to cellular gene delivery, as surface charge density plays a role in controlling the extent of endosomal escape. It is reported that higher generation dendrons, although binding DNA less strongly than the self-assembling lower generation dendrons, are more effective for transfection. The impact of the lipophilic group at the focal point is less significant for the DNA binding ability of these larger dendrons, which is predominantly controlled by the spermine surface groups, but it does modify the levels of gene transfection. Significant synergistic effects on gene delivery were observed when employing combinations of the dendrons and polyethyleneimine (PEI, 25 kDa), with transfection becoming possible at low loading levels where the two components would not transfect individually, giving practically useful levels of gene delivery.

Catalytic properties of dendron–OMS hybrids

The synthesis and catalytic testing of several dendron–ordered mesoporous silica hybrids are reported. These materials are active in both the nitroaldol (Henry) reaction and the transesterification of glyceryl tributyrate to afford methyl esters. In both reactions it is observed that dendrons terminated with primary amines are more catalytically active than samples containing dendrons terminated with secondary amines. On a mmol nitrogen per gram of silica basis, the first generation dendrons are the most active for both chemistries, and the SBA-15 samples display a higher activity than the MCM-41 samples. The pore-size effect observed is consistent with significant diffusion resistance in the MCM-41 samples. The activity trend observed in the SBA-15 materials is consistent with decreased cooperative effects between the amines and surface silanols as the dendrons become larger. Clear trends are observed indicating that higher generation dendrons are more selective to alcohol formation in the Henry reaction. The dendron catalysts are much more active and stable than simple amines attached to silica in the transesterification of triglycerides. Preliminary results shown indicate that these materials can also catalyze more demanding chemistries, an example of which is the Aldol condensation of 5-(hydroxymethyl)furfural and acetone. The results shown indicate that dendron–OMS hybrids can serve as effective solid base catalysts for a diverse range of chemistries.

Novel Synthesis of Amphiphilic Dendrons by the Double-Stage Convergent Method

A series of amphiphilic dendrons (G1-G4) have been designed and synthesized, which have a highly branched aliphatic hydrocarbon skeleton and a hydrophilic hydroxyl functionality to enable conjugation with other substrates. The higher generation dendrons (G3 and G4) were synthesized by a double-stage convergent method, which shortened the synthetic route significantly and provided the products in an efficient manner. The key branching step involved a double alkyl-metal addition to an ester functionality followed by deoxygenation of a resulting tertiary alcohol by triethylsilane.

Dendronized organic–inorganic nonlinear optical hybrid materials with homogeneous morphology

To obtain excellent thermal stability, a series of dendronized organic–inorganic hybrids were synthesized and characterized. Dendronized alkoxysilane dyes were prepared via the ring opening addition reaction of azetidine-2,4-dione of chromophore-containing dendrons, with 3-aminopropyltriethoxysilane. Subsequently, the precursor, dendronized alkoxysilane dyes could be hydrolyzed and copolymerized with phenyltriethoxysilane (PTEOS) with the weight ratios of 1:1, 1:3, 1:5 and 1:7 in the presence of water and formic acid. After curing and poling process, organic–inorganic hybrid thin films with homogeneous morphology were obtained. Electro-optical (EO) coefficients (r33) of 2.9–13.0pm/V were achieved. Due to the site-isolation effect, the sample with high generation dendrons possessed a higher EO coefficient/dye content ratio. In addition, because of the improved miscibility between organic and inorganic segments due to highly branched hydrogen bonding-rich dendrons, NLO polymers with waveguide properties ranging from 3.2 to 4.2dB/cm at 1310nm were obtained. These dendronized organic–inorganic NLO hybrids also show greatly enhanced temporal stability at 100°C.

Nonlinear optical polyimides consisting of chromophore‐containing dendrons with site‐isolation effect

AbstractTo investigate the dendritic structure effects on the electro‐optical (EO) coefficients and thermal stability of the nonlinear optical (NLO) active materials, a bifunctional compound, IDD (4‐isocyanato‐4′(3,3‐dimethyl‐ 2,4‐dioxo‐acetidino)‐diphenylmethane) was used as a building block to synthesize a series of novel NLO chromophore‐containing dendritic structures including Generation 0.5 (G0.5) to Generation 3 (G3). The glass transition temperatures (Tg) of G1–G3 dendrons were in the range of 76–116°C, whereas only the G0.5 dendron exhibited a melting temperature (Tm), 98°C. Moreover, a series of NLO‐active guest–host systems ranging from polyimide‐G0.5 (PI‐G0.5) to polyimide‐G3 (PI‐G3) were prepared by blending 20 wt% chromophore‐containing dendron with a high Tg polyimide. EO coefficients ranged from 6.1 to 12.9 pm/V. The r33/dye content ratio increased with increasing generation of dendron‐containing polyimide samples. Particularly, the improvement in r33/dye content ratio of PI‐G2.5 sample tripled as compared to that of the guest–host sample with Disperse Red 1. Excellent temporal stability of PI‐G0.5 and PI‐G1.5 at 80°C was obtained. Moreover, waveguide properties for NLO polymers containing higher generation dendrons (3.1–3.6 dB/cm at 830 nm) were also obtained. Copyright © 2008 John Wiley &amp; Sons, Ltd.