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 Gold‐Nanoparticle‐Cored Dendrimers Stabilized by Metal–Carbon Bonds

Synthesis and characterization of gold‐nanoparticle‐cored dendrimers (NCDs), in which the dendrons are attached to the gold core through gold–carbon bonds, are described. Synthesis of these materials involved the simultaneous reduction of HAuCl₄ and a Fréchet‐type dendron with a diazonium group at the focal point, all in an organic solvent such as toluene. These materials possess a nanometer‐sized gold core surrounded by a shell of polyaryl ether dendrons, which are connected radially to the core. The NCDs were characterized by TEM, thermogravimetric analysis (TGA), and IR, UV, and NMR spectroscopic techniques. Average particle diameter of the NCDs ranged from 4.7 to 5.5 nm for the different generations. All NCDs exhibit the characteristic plasmon absorption of gold nanoparticles at 520 nm. Average numbers of dendrons per NCD in AuG_n were calculated using results from TGA and TEM studies. Multiple layering of the dendrons is proposed as a possible reason for the high dendron/NCD value.     

A Dendrimer Chiroptical Switch Based on the Reversible Intramolecular Photoreaction of Anthracene and Benzene Rings

A series of Fréchet‐type dendrimers with 9‐benzyloxymethylanthracene cores were synthesized and characterized. The chiral source for the dendrimers was an (S)‐2‐methyl‐1‐butoxy group in the 3‐position of the benzene ring. Irradiation at 366 nm of a dilute benzene solution led to the formation of two diastereomers (1:1) through a quantitative intramolecular [4π+4π] cycloaddition between the central anthracene ring and the neighboring benzene ring. The process can be reversed with 254 nm UV light or heat. The benzene rings in the dendrons work as a light‐harvesting system. The optical rotation values measured for the reversible process showed fatigue resistance. Thus, a promising new type of chiroptical switch has been created that has optical rotation values as output signals.     

Synthesis of Polyisoprene Terpenoid Dendrons and their Applications in Oligo(phenylene ethynylene)s as “Shells”

The novel double‐stage convergent synthesis of a new class of polyisoprene terpenoid (PIPTP) dendrons is described. PIPTP dendrons bear a highly branched aliphatic hydrocarbon skeleton and a hydrophilic hydroxy focal point functionality. These dendrons have the specific formula C_(5×2^G+1_‐5)H_(5×2^G+2_‐8)O, and each dendritic layer is constructed from an isoprene unit. The key branching steps involve a double alkyl‐metal addition to an ester functionality, followed by deoxygenation of the resulting tertiary alcohol by triethylsilane and trifluoroacetic acid, then hydrogenation or hydrogenolysis. The dendrons were also attached to oligo(phenylene ethynylene)s (OPEs) so as to function as protective shells to allow fine tuning of the nanoscopic environment around the OPE moiety, and to exert precise control of the packing density and intermolecular interaction between the OPE cores. Fluorescence quantum yield data reveal that the OPE core is better encapsulated by the PIPTP dendrons than by Fréchet dendrons.     

Synthesis of Dendritic BINAP Ligands and Their Applications in Asymmetric Hydrogenation

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Host-guest complexes between an aromatic molecular tweezer and symmetric and unsymmetric dendrimers with a 4,4'-bipyridinium core

We have investigated the spectroscopic and electrochemical behavior of symmetric and unsymmetric first-, second-, and third-generation dendrimers comprising an electron-acceptor 4,4'-bipyridinium core (viologen type) and electron-donor 1,3-dimethyleneoxybenzene (Fréchet-type) dendrons. The quite strong fluorescence of the symmetrically and unsymmetrically disubstituted 1,3-dimethyleneoxybenzene units of the dendrons is completely quenched as a result of donor-acceptor interactions that are also evidenced by a low-energy tail in the absorption spectrum. In dichloromethane solution, the 4,4'-bipyridinium cores of the investigated dendrimers are hosted by a molecular tweezer comprising a naphthalene and four benzene components bridged by four methylene units. Host-guest formation causes the quenching of the tweezer fluorescence. The association constants, as measured from fluorescence and (1)H NMR titration plots, (i) are of the order of 10(4) M(-1), (ii) decrease on increasing dendrimer generation, and (iii) are slightly larger for the unsymmetric than for the symmetric dendrimer of the same generation. The analysis of the complexation-induced shifts of the temperature-dependent (1)H NMR signals of the host and guest protons confirms that the bipyridinium core is positioned inside the tweezer cavity and allows the conclusions that (i) shuttling of the tweezer from one to the other pyridinium ring is fast (DeltaG < 10 kcal/mol), (ii) in the case of the unsymmetric dendrimers, the less substituted pyridinium ring is preferentially complexed in apolar solvents, and (iii) complexation of the 4,4'-bipyridinium core proceeds by clipping for the symmetric dendrimers and by threading in the case of unsymmetric ones. Host-guest formation causes a displacement of the first reduction wave of the 4,4'-bipyridinium unit toward more negative potential values, whereas the second reduction wave is unaffected. These results show that the host-guest complexes between the tweezer and the dendrimers are stabilized by electron donor-acceptor interactions and can be reversibly assembled/disassembled by electrochemical stimulation.     

Codendronized polymers pendent with alternating dendritic wedges

Codendronized polymers pendent with Fréchet‐type poly(benzyl ether) dendron and polyester dendron alternating structure have been produced by combining macromonomer and graft‐from approach. Alternating copolymerization of the styryl dendrons of three generations and N‐(2‐hydroxyethyl)maleimide was used to prepare the polymer backbone bearing the first kind of dendritic wedges, then polyester dendrons were grown up from the pendant hydroxy groups through iterative esterification and deprotection reactions. Then, a kind of codendronized polymer bearing different dendritic wedges with an alternating structure was thus obtained. Since the pendent dendrons were different and each of them was well‐defined, such codendronized polymer can be a multicompartment wormlike molecule. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3994–4001, 2007     

Dendrimer Disassembly in the Gas Phase: A Cascade Fragmentation Reaction of Fréchet Dendrons

The mass spectrometric characterization of Fréchet‐type dendrons is reported. In order to provide the charges necessary for electrospray ionization, dendrons bearing an OH group at the focal point can be deprotonated and observed in the negative ion mode. Alternatively, the corresponding bromides can be converted to quaternary ammonium ions that can easily be detected in the positive mode. If the latter ions are subjected to collision‐induced dissociation experiments, a fragmentation cascade begins with the dissociation of the focal amine. The focal benzyl cation quickly decomposes in a fragmentation cascade from the focal point to the periphery until the peripheral benzyl (or naphthylmethyl) cations are formed. Five different mechanisms are discussed in detail, three of which can be excluded based on experimental evidence. The cascade fragmentation is reminiscent of self‐immolative dendrimers.     

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.     

New Calix[4]arene‐Cored Peripherally Functionalized Dendrimers: Synthesis and Conformational Characteristics

New calixarene‐based dendrimers, containing calix[4]arene as the core and different generations of Fréchet‐type poly(benzyl ether) dendrons as building blocks, which possess either Br‐atoms or COO^tBu groups at their surface were synthesized and presented herein for the first time. The new calix[4]arene‐cored dendritic macromolecules were fully characterized and found to prefer strictly the cone conformation.     

Redox active, hybrid dendrimers containing Fréchet- and Newkome-type blocks

A new series of dendrimers was prepared by covalently attaching a Newkome dendron, a Fréchet dendron, and a redox active, aminoferrocene group to a central triazine core. Growth of the Newkome dendron has a more pronounced effect on the half-wave potential for the one-electron oxidation of the ferrocene residue than growth of the Fréchet dendron. All dendrimers show reversible or quasireversible voltammetric behavior at scan rates in the range 0.10-2.0 V s-1.     

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.     

Synthesis and encapsulation properties of dendronized polymer with Fréchet‐type dendrons peripherally decorated by carboxylic acid functionalization

A new carboxylic acid‐terminated dendronized polymer (denpol), constructed with linear chain attaching Fréchet‐type dendrons at each repeat unit, has been designed and synthesized through a combination of macromonomer route and hydrolysis reaction. The resulting denpol exhibits excellent solubility in aqueous solution for pH ≥ 6, and significantly the denpol also encapsulates various aromatic molecules efficiently. The results of UV–vis and fluorescence spectra indicate that hydrophobic and π‐π interactions bring into effect between the water‐insoluble organic molecules and the denpol. Moreover, the photoisomerization of azobenzene solubilized in denpol aqueous solution was investigated, which indicated that trans‐to‐cis and cis‐to‐trans conversions were first‐order reactions. The enhancement of photoisomerization property may attribute to the proper microenvironment in the denpol. Therefore, the denpol is expected to be a potential candidate as amphiphilic unimolecular container. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 4564–4574, 2008     

Synthesis of Fréchet-type dendritic homotriptycenes

A rapid and efficient synthesis of novel dendrimer homotriptycenes is presented. The dendronized 9,10-dihydroanthracen-9-ols 4, having high electron densities in the benzene rings of the Fréchet-type dendrons, exhibited in the presence of acid a quantitative transannular ring closure to the corresponding dendritic homotriptycenes. The electron-donating Fréchet-type dendrons enabled the intramolecular FC alkylation by a regioselective 1,7-elimination of H2O.     

The Effect of Incorporating Fréchet Dendrons into Rotaxanes and Molecular Shuttles Containing the 1,2‐Bis(pyridinium)ethane⊂[24]Crown‐8 Templating Motif

Fréchet‐type dendrons (G0–G3) were added as both axle stoppering units and cyclic wheel appendages in a series of [2]rotaxanes, [3]rotaxanes, and molecular shuttles that employ 1,2‐bis(pyridinium)ethane axles and 24‐membered crown ethers wheels. The addition of dendrimer wedges as stoppering units dramatically increased the solubility of simple [2]rotaxanes in nonpolar solvents. The X‐ray structure of a G1‐stoppered [2]rotaxane shows how the dendritic units affect the structure of the interlocked components. Increased solubility allows observation of how the interaction of dendritic units on separate components in interlocked molecules influences switching properties and molecular size. In a series of [2]rotaxane molecular shuttles incorporating two recognition sites, it was demonstrated that an increase in generation on either the stoppering unit or cyclic wheel could influence both the rate of shuttling and the site preference of the wheel on the axle.     

Hybrid dendritic–linear graft copolymers: Steric considerations in “coupling to” approach

A “coupling to” approach was developed for the synthesis of hybrid dendritic–linear block copolymers. Fréchet‐type polyether dendrons were prepared by the convergent growth approach and coupled with well‐defined functionalized polystyrene backbones prepared by living free radical procedures. The subtle interplay between the degree of functionalization present in the backbone and the size of the dendritic fragment led to incomplete reactions as steric crowding along the backbone increased. This resulted in globular hybrid macromolecules instead of the extended rods typically formed from the polymerization of dendritic macromonomers. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 1033–1044, 2000     

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

The synthesis and characterization of four dendron‐containing tetraphenylethylenes (TPEs), 1₁ – 1₄ , were synthesized, along with a TPE compound that contained four OCH₂Ph groups (referred to as 1₀ ) 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: 1₁ < 1₂ < 1₃ < 1₄ . 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: 1₁ < 1₂ < 1₃ < 1₄ . 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.     

Synthesis of Fréchet type dendritic benzyl propargyl ether and Fréchet type triazole dendrimer

Fréchet type dendritic benzyl propargyl ethers were synthesized by the reaction of propargyl bromide with the corresponding Fréchet type dendritic benzyl alcohol. A propargyl focal point functionalized dendrons were applied for the construction of symmetric and unsymmetric dendrimers containing 1,2,3-triazole rings as connectors via click chemistry with a tripodal azide core or a azide focal point functionalized Fréchet type dendrons.     

Polymerization of styrenes carrying dendrons of the first,second and third generation

The synthesis of styrene monomers 5 (G-1,2,3) with Fréchet-type dendrons of the first, second and third generation, and their radically initiated polymerization to result in high molecular weight dendrimers 6 (G-1,2,3) are reported. First light-scattering investigations using 6 (G-2) show that this polymer is best described as a Gaussian chain.     

Photophysical properties of 9,10-disubstituted anthracene derivatives in solution and films

We have carried out absorption, time-resolved fluorescence, and fluorescence quantum yield measurements of four new soluble anthracene derivatives. They show natural radiative lifetimes in the range of 2.5-4.4 ns, which is 5-10 times shorter than those reported for unsubstituted anthracene. The 9,10-bis(phenylethynyl)anthracene (BPEA) derivatives show the largest fluorescence transition dipoles, which is attributed to extended π-conjugation between anthracene and phenyls through acetylene linkages. Spin-cast films of the BPEA derivatives show strong fluorescence quenching by weakly emitting low energy excitations, which is attributed to excimer-like traps. Quenching is significantly reduced when bulky dendrons are attached so that they give maximum coverage of the emitting chromophore and prevent their aggregation. The results show that anthracene derivatives can be developed into efficient solution-processable fluorescent emitters for the blue and green spectral regions.