Solid-state Photoluminescence Quantum Yields Research Articles

An efficient solution-processable hybridized local and charge-transfer (HLCT)-based deep-red fluorescent emitter for simple structured non-doped OLED

The development of highly efficient deep-red fluorescent emitters is still a challenging task due to their intrinsic low bandgap characteristics resulting in low fluorescence emission in solid-state. Moreover, most of efficient deep-red organic light-emitting diodes (OLEDs) have complex device structures and are fabricated by high-cost vacuum deposition techniques. Herein, a novel solution-processable hybridized local and charge-transfer (HLCT) deep-red fluorescent molecule, TPA-NZF, is designed and synthesized as an emitter for low-cost and simple-structured OLEDs. TPA-NZF comprises a strong electron-deficient naphthothiadiazole (NZ) functionalized with triphenylamine (TPA) as a donor and dioctylfluorene as a solubilizing moiety. The photophysical results and theoretical calculations reveal a strong donor-acceptor feature and deep-red fluorescent emission with a solid-state photoluminescence quantum yield as high as 44%, decent hole-transporting mobility, good film morphology, and thermal and electrochemical stabilities. TPA-NZF is successfully fabricated as a solution-processed non-doped emitter in simple structured OLEDs. The device shows excellent electroluminescence (EL) performance (maximum external quantum efficiency (EQEmax) of 3.59%) and a deep-red emission with CIE coordinates of (0.66, 0.33).

Two-photon excited fluorescence from ground-state charge-transfer cocrystals of acridine and 1,2,4,5-tetracyano-benzene

Near-infrared two-photon absorption (TPA) molecules designed based on intramolecular charge-transfer (CT) interactions have been widely investigated during the last few decades; however, studies on supramolecular TPA materials based on intermolecular CT interactions are quite rare. In this work, cocrystals of acridine and 1,2,4,5-tetracyano-benzene were successfully prepared by self-assembly. The cocrystals show yellow emission centered at ∼540 nm with a solid-state photoluminescence quantum yields (PLQY) of 22.48%. Two-photon excited fluorescence (TPEF) measurements show that the cocrystals display wide-window TPEF that is absent in their individual components. Optical absorption analysis indicate that the fluorescence is originated from excitation from the ground states to CT exciton states instead of exciton states of donor or acceptor molecules. This work may facilitate further two-component nonlinear optical material design and applications.

Deep Blue Fluorescent Material with an Extremely High Ratio of Horizontal Orientation to Enhance Light Outcoupling Efficiency (44%) and External Quantum Efficiency in Doped and Non-Doped Organic Light-Emitting Diodes

A novel bis-4Ph-substituted 9,10-dipehnylanthracene deep blue [1931 CIE (0.15, 0.08)] fluorescent compound, AnB4Ph, has been synthesized and characterized for organic light-emitting diode (OLED) applications. Our experimental study of AnB4Ph excludes the possibility of triplet-triplet annihilation, hybridized local and charge transfer, or thermally activated delayed fluorescent characteristics of the material. Since the solid-state photoluminescence quantum yield of AnB4Ph was determined to be 48%, assuming a 100% for the charge recombination efficiency, the light outcoupling efficiency (ηout) of an AnB4Ph non-doped OLED achieving an external quantum efficiency (EQE) of 5.3% is at least 44%, which is more than twofold higher than 20% for conventional OLEDs. Both grazing incidence wide-angle X-ray scattering (GIWAXS) and angle-dependent photoluminescence (ADPL) measurements reveal AnB4Ph having a high value of order parameter (SGIWAXS) of 0.61 for a ππ stacking along the normal direction and an orientation order parameter (SADPL) for a horizontal emitting dipole moment of -0.50 or Θ (horizontal-dipole ratios) of 100%, respectively. Otherwise, a refractive index (n) measurement provides a n = 1.80 for AnB4Ph thin films. Based on ηout = 1.2 × n-2, the calculated ηout is 37%, which is also in accordance with the results of GIWAXS and ADPL. We have also fabricated the classical fluorescent DPAVBi-doped AnB4Ph OLEDs, which display a true blue [1931 CIE (0.15 and 0.16)] electroluminescence with a high efficiency (EQE = 6.9%), surpassing the conventional ∼5% EQE. Based on an ηout of 42% for DPAVBi-doped AnB4Ph OLEDs, our studies suggest that the extremely horizontally aligned AnB4Ph host material exerts the same horizontal alignment on the DPAVBi dopant molecules.

Sandwich-Type Uranyl Phosphate-Polyoxometalate Cluster Exhibiting Strong Luminescence.

A pure inorganic uranyl phosphate-polyoxometalate of Na17{Na@[(SbW9O33)2(UO2)6(PO3OH)6]}·xH2O (abbreviated as Na@U6P6, with x ≈ 46) featuring a sandwich-type structure was prepared using Keggin-type trilacunary [α-B-SbW9O33]9- units as building blocks, which were formed in situ by SbCl3 and Na2WO4·2H2O. Crystal structural analysis showed that six UO22+ cations and six PO3OH2- anions generated a wheel-like cluster unit with a Na+ center ([Na@(UO2)6(PO3OH)6]+) that is stabilized by two [α-B-SbW9O33]9- units. Na@U6P6 displayed a solid-state photoluminescence quantum yield of 33% at 300 K. The temperature-dependent fluorescence emission spectra showed that Na@U6P6 has temperature-sensitive fluorescence in which its emission intensity decreased by 77% as the temperature increased from 200 to 300 K. These results suggest that such uranyl phosphate-polyoxometalate clusters could serve as potential temperature-sensitive molecular materials.

Tailoring Color-Tunable Dual Emissions of Mn2+-Alloyed Two-Dimensional Perovskite Quantum Wells

While manganese (Mn2+)-doped chalcogenide and perovskite CsPbX3 nanocrystals (NCs) have been extensively investigated, the research of color-tunable dual-emissive Mn2+-incorporated two-dimensional (2D) quantum wells (QWs) is limited. Here, we present alloyed Mn:(PEA)2PbBr4 2D perovskite QWs, achieving efficient dual-color emissions with high energy transfer efficiency (ΦET = 56%) and solid-state photoluminescence quantum yield (PLQY = 54%). Importantly, excitation and temperature are demonstrated as two efficient approaches to precisely modulate color-tunable dual emissions with excellent reversibility. The results indicate possible applications of such materials in photo-/thermal switchable markers and efficient thermometers for biomedical imaging and diagnostic investigations.

Highly luminescent and catalytically active suprastructures of magic-sized semiconductor nanoclusters.

Metal chalcogenide magic-sized nanoclusters have shown intriguing photophysical and chemical properties, yet ambient instability has hampered their extensive applications. Here we explore the periodic assembly of these nanoscale building blocks through organic linkers to overcome such limitations and further boost their properties. We designed a diamine-based heat-up self-assembly process to assemble Mn2+:(CdSe)13 and Mn2+:(ZnSe)13 magic-sized nanoclusters into three- and two-dimensional suprastructures, respectively, obtaining enhanced stability and solid-state photoluminescence quantum yields (from <1% for monoamine-based systems to ~72% for diamine-based suprastructures). We also exploited the atomic-level miscibility of Cd and Zn to synthesize Mn2+:(Cd1-xZnxSe)13 alloy suprastructures with tunable metal synergy: Mn2+:(Cd0.5Zn0.5Se)13 suprastructures demonstrated high catalytic activity (turnover number, 17,964 per cluster in 6 h; turnover frequency, 2,994 per cluster per hour) for converting CO2 to organic cyclic carbonates under mild reaction conditions. The enhanced stability, photoluminescence and catalytic activity through combined cluster-assembly and metal synergy advance the usability of inorganic semiconductor nanoclusters.

Fabrication of Quantum Dots@Metal–Organic Frameworks Nanocomposites By Direct Surface Modification

Semiconductor quantum dots (QDs), have been attracting much attention as the next generation of light-emitting materials due to their unique properties, such as their broad absorption range and narrow band-edge photoluminescence (PL) with high emission quantum yield. Since, in particular, precise controllability of luminescent color by changing the QD size is quite attractive and useful, they have been practically used in devices such as back light films of liquid crystal display. Although highly dense QDs are required for color filters and on chip light sources with high efficiency, Förster resonance energy transfer (FRET) to non-fluorescent QDs is inevitable when each QDs adjacently exists, resulting in large decline in quantum yields (QY). One of the reasons to generate non-fluorescent QDs is the accumulation of damage over time to the organic ligands attached to the surface as a passivation layer. To overcome the QD degradation derived from organic ligands desorption, the development of robust and easily grown surface protective materials is important.Metal–organic frameworks (MOFs), which are a new class of microporous crystalline materials formed by the self-assembly of metal ions and organic linkers, are promising candidates as new surface modification materials for QDs. Owing to their versatile architecture and adjustable functionality derived from the combination of their components, MOFs possess high variety of applications, such as gas storage, catalysts, and semiconductors. Among them, the combinations of MOFs with other categories of nanomaterials, such as metal nanoparticles, have attracted much attention lately to give further functionalities to MOFs. Therefore, if MOFs are utilizable as new classes of surface modifiers for fluorescent QDs, not only the stability improvement but also new functionality appearance of QDs are expected.In this study, the aforementioned possibility of MOFs toward fluorescent QDs was investigated. CdSe/CdS core/shell QDs were attempted to be covered by zeolitic imidazolate framework-8 (ZIF-8) through a direct link between the two without using any other bonding materials like polymers. The QDs were observed to be fully incorporated into the ZIF-8 crystal and were photoluminescent with a solid-state PL QY as high as 40%. Narrow band-edge emission unique to the QDs was maintained during and after the modification with ZIF-8. In addition, we visually confirmed the structure of ZIF-8 crystals gradually transformed from a roughly spherical shape to rhombic dodecahedra (Fig. 1). The incorporation of a single QD into a ZIF-8 crystal was also successfully accomplished by changing the ligands on the starting QDs. To evaluate the potential of ZIF-8 as a protecting shell for QDs, 1,4-benzoquinone, one of the efficient electron acceptors that can quench the PL from CdSe/CdS core/shell QDs, was added to the solution of pyridine-capped CdSe/CdS core/shell QDs as well as a suspension of CdSe/CdS QD@ZIF-8 composite. As shown in Fig. 2, the addition of 1,4-benzoquinone hardly affected the PL of the QDs after ZIF-8 modification, indicating complete incorporation of the QDs into ZIF-8 crystals. Figure 1

Preserving High-Efficiency Luminescence Characteristics of an Aggregation-Induced Emission-Active Fluorophore in Thermostable Amorphous Polymers.

Luminophores usually suffer from luminescent quenching when introduced into a polymer backbone or side chain, which leads to the inefficient luminescence or even no luminescence of the polymer. In this work, alicyclic imide rings were found to be capable of balancing the donor-acceptor properties between the rigid spacer and the aggregation-induced emission-active fluorophore in light-emitting polymers. Along with the nonplanar and rigid emitter, the suppressed intramolecular charge-transfer effect and interchain disturbance can efficiently preserve the luminescence characteristics of the active center, resulting in high solid-state photoluminescence quantum yields of up to 89%. The amorphous polyimides exhibit excellent thermal properties, such as high glass transition temperature (Tg) values (398 °C) and high thermal decomposition temperature (Td) values (538 °C). As far as we know, these luminescent polymer materials are of excellent heat resistance with the highest luminescence efficiency reported. The results have significant impact for the precise prediction of the optical properties of light-emitting polymers by appropriate monomer design, providing controllable ways for synthesizing high thermal stability polymeric materials with efficient fluorescence properties.

Organolithium-Mediated Postfunctionalization of Thiazolo[3,2-c][1,3,5,2]oxadiazaborinine Fluorescent Dyes.

An effective method for transition-metal-free postfunctionalization of thiazolo[3,2-c][1,3,5,2]oxadiazaborinine dyes via direct lithiation of the 1,3-thiazole ring was developed. The reaction allows valuable regioselective C–H modification of these N,O-chelated organoboron chromophores incorporating different groups, including C-, Hal-, Si-, S-, Se-, and Sn-substituents. As a result, a library of novel fluorescent 1,3-thiazole-based organoboron complexes has been synthesized and characterized. The influence of the donor/acceptor strength of the substituent E on the photophysical properties has been established. The compound with a bulky lipophilic substituent (SnBu3) exhibits a relatively high solid-state photoluminescence quantum yield of 44%.

Molecular engineering on all ortho-linked carbazole/oxadiazole hybrids toward highly-efficient thermally activated delayed fluorescence materials in OLEDs

The highest efficiency thermally activated delayed fluorescence (TADF) emitters in OLEDs are mostly based on twisted donor/acceptor (D/A) type organic molecules. Herein, we report the rational molecular design on twisted all ortho-linked carbazole/oxadiazole (Cz/OXD) hybrids with tunable D-A interactions by adjusting the numbers of donor/acceptor units and electron-donating abilities. Singlet-triplet energy bandgaps (ΔEST) are facilely tuned from ∼0.4, 0.15 to ∼0 eV in D-A, D-A-D to A-D-A type compounds. This variation correlates well with triplet-excited-state frontier orbital spatial separation efficiency. Non-TADF feature with solid state photoluminescence quantum yield (PLQY) < 10% is observed in D-A type 2CzOXD and D-A-D type 4CzOXD. Owing to the extremely low ΔEST for efficient reverse intersystem crossing, strong TADF with PLQY of 71%–92% is achieved in A-D-A type 4CzDOXD and 4tCzDOXD. High external quantum efficiency from 19.4% to 22.6% is achieved in A-D-A typed 4CzDOXD and 4tCzDOXD.

Structure-Directing Effects of Counterions in Uranyl Ion Complexes with Long-Chain Aliphatic α,ω-Dicarboxylates: 1D to Polycatenated 3D Species.

Nine uranyl ion complexes were synthesized under (solvo-)hydrothermal conditions using α,ω-dicarboxylic acids HOOC-(CH2) n-2-COOH (H2C n, n = 6-9) and diverse counterions. Complexes [PPh4][UO2(C6)(NO3)] (1) and [PPh4][UO2(C8)(NO3)] (2) contain zigzag one-dimensional (1D) chains, with further polymerization being prevented by the terminal nitrate ligands. [PPh3Me][UO2(C7)(HC7)] (3) crystallizes as a 1D polymer with a curved section, with hydrogen bonding of the uncomplexed carboxylic groups giving rise to formation of 3-fold interpenetrated two-dimensional (2D) networks. [PPh4][H2NMe2][(UO2)2(C7)3] (4) and [PPh3Me]2[(UO2)2(C8)3] (5) contain 1D chains, either ladder-like or containing doubly bridged dimers, while [PPh3Me]2[(UO2)2(C9)3]·2H2O (6) displays interdigitated, strongly corrugated honeycomb 2D nets. Ladder-like 1D polymers in [Cu( R,S-Me6cyclam)][(UO2)2(C7)2(C2O4)]·4H2O (7) are associated into layers by the hydrogen bonded counterions, whereas the [Ni(cyclam)]2+ moieties are part of the 2D polymeric arrangement in [(UO2)2(C7)2(HC7)2Ni(cyclam)]·2H2O (8) because of axial coordination of the nickel(II) center, with hydrogen bonding mediated by water molecules generating a three-dimensional (3D) net. [(UO2)2K2(C7)3(H2O)]·0.5H2O (9) contains convoluted uranyl dicarboxylate 2D subunits, which generate a 3D framework through 2D → 3D parallel polycatenation similar to that previously found in [NH4]2[(UO2)2(C7)3]·2H2O; further linking of these subunits is provided by bonding of the potassium cations to carboxylate and uranyl oxido groups. The solid-state emission spectra of complexes 1-6 and 9 display maxima positions typical of hexacoordinated uranyl carboxylate complexes, but uranyl luminescence is quenched in 7. A solid-state photoluminescence quantum yield of 11.5% has been measured for complex 1, while those for compounds 3-6 and 9 are in the range of 2.0-3.5%.

Chiral Discrete and Polymeric Uranyl Ion Complexes with (1 R,3 S)-(+)-Camphorate Ligands: Counterion-Dependent Formation of a Hexanuclear Cage.

Reaction of (1 R,3 S)-(+)-camphoric acid (H2cam) with uranyl ions under solvo-hydrothermal conditions and in the presence of bulky countercations gave five chiral complexes of varying dimensionality. [Cu( R,S-Me6cyclam)][UO2(Hcam)2(HCOO)2] (1) and [Ni( R,S-Me6cyclam)][UO2(cam)(HCOO)2] (2), in which the formate coligand is formed in situ, involve very similar countercations, but 1 is a discrete, mononuclear complex, whereas 2 crystallizes as a one-dimensional (1D) coordination polymer, and NH-bond donation by the macrocyclic ligand of the countercation complexes is present in both. [Co(en)3][(UO2)4(cam)( R,R-tart)2(OH)]·3H2O (3), in which en is ethylenediamine and H4 R,R-tart is R,R-tartaric acid, contains three enantiomerically pure chiral species, and it displays a two-dimensional (2D) arrangement, with the countercation again involved in NH-bond donation. While [PPh4][UO2(cam)(NO3)] (4) is a 1D polymer, [PPh3Me]3[NH4]3[(UO2)6(cam)9] (5) is a discrete, homochiral, and homoleptic hexanuclear cage with C3 point symmetry and a trigonal prismatic arrangement of the uranium atoms. This cage differs from the octanuclear, pseudocubic uranyl camphorate species previously described, thus providing an example of modulation of the cage size through variation of the structure-directing counterions. The cage in 5 is closely associated with three PPh3Me+ cations, two of them outside and with their methyl group directed toward the prism basis center, and one inside the cage cavity. While complex 5 is nonluminescent, complexes 1 and 4 have emission spectra in the solid state typical of equatorially hexacoordinated uranyl complexes. Solid-state photoluminescence quantum yields of 2 and 23% have been measured for complexes 1 and 4, respectively.

Fluorene-Based Conjugated Microporous Polymers: Preparation and Chemical Sensing Application.

Conjugated microporous polymers (CMPs) with strong fluorescence are great candidates for optoelectronic applications such as photocatalysis and chemical sensing. A series of novel fluorene-based conjugated microporous polymers (FCMPs) with different electronic structures are prepared by Yamamoto coupling reactions using rationally designed monomers. The FCMPs show a high degree of microporosity, decent specific surface areas, and variable fluorescence. FCMP3, which possesses a triazine knot in the network, exhibits the highest specific surface area of 489 m2 g-1 , the largest pore volume of 0.30 cm3 g-1 , and the highest solid-state photoluminescence quantum yield of 11.46%. Chemical sensing performance of FCMPs is studied using a range of nitroaromatic compounds as the analytes. Among the FCMPs, FCMP3 exhibits the highest Stern-Volmer constants of 2541, 4708, and 5241 m-1 for the detection of nitrobenzene, 4-nitrotoluene, 2,4-dinitrotoluene, respectively, which are comparable to the detecting efficiency of the state-of-the-art CMP-based sensing agents.

Very High Solid State Photoluminescence Quantum Yields of Poly(tetraphenylethylene) Derivatives.

Five different poly(arylene-diarylvinylene)s have been synthesized by reductive polyolefination starting from the corresponding bis(α,α-dichlorobenzyl)-substituted monomers and dicobaltoctacarbonyl as reducing agent. The resulting polymers all contain main chain tetraphenylethylene units. Thanks to the aggregation-induced emission effect, the corresponding polymer films show remarkably high photoluminescence quantum yields (PLQYs) of 32%-73%. The polymer with the highest PLQY is tested as solid state sensing material for the PL-quenching-based detection of nitroaromatic analytes (1,3,5-trinitrobenzene as prototypical analyte).

Direct evidence for secondary interactions in planar and nonplanar aromatic π-conjugates and their photophysical characteristics in solid-state assemblies.

Direct evidence for non-covalent secondary interactions in planar and nonplanar aromatic π-conjugates and their solid-state assemblies is established. A series of horizontally, vertically, and radially expanded oligo(phenylenevinylene)s (H-OPVs, V-OPVs, and R-OPVs, respectively) were designed with a fixed π-core and variable alkyl chain lengths on the periphery. Single-crystal structures of the OPVs were resolved to trace the secondary interactions that direct the solid-state self-organization and molecular packing of the chromophores. The H-OPVs were found to be planar, and they did not show any secondary interactions in the crystal lattices. The V-OPVs and R-OPVs were found to be nonplanar and to exhibit multiple CH/π hydrogen-bonding interactions among aryl hydrogen donors and acceptors. The enthalpies of the melting and crystallization transitions revealed that the planar H-OPVs are highly crystalline compared with the nonplanar R-OPVs and V-OPVs. Polarized light microscopy studies revealed the formation of one-dimensional nematic mesophases in H-OPVs. The absolute solid-state photoluminescence quantum yields (PLQYs) of the OPVs were determined using an integrating sphere setup. The highly packed H-OPVs showed low PLQYs compared with those of the weakly packed V-OPVs and R-OPVs. Time-resolved fluorescence decay measurements revealed that the excited-state decay dynamics of highly packed H-OPVs was much faster with respect to their low PLQYs. The decay profiles were found to be relatively slow (with higher life time (τ)) in the V-OPVs and R-OPVs. A field-effect transistor (FET) device was constructed for an OPV sample that showed a hole carrier mobility in the range of 10(-5) cm(2) V(-1) s(-1). The present investigation thus provides a new opportunity to trace the role of secondary interactions on π-conjugated mesophase self-assemblies and their solid-state emission and FET devices, more specifically based on OPV chromophores.

Spirobifluorene/sulfone hybrid: Highly efficient solution-processable material for UV–violet electrofluorescence, blue and green phosphorescent OLEDs

A high efficient UV–violet emission type material bis[4-(9,9′-spirobifluorene-2-yl)phenyl] sulfone (SF-DPSO) has been synthesized by incorporating electron deficient sulfone and morphologically stable spirobifluorene into one molecule. The steric and bulky compound SF-DPSO exhibits an excellent solid state photoluminescence quantum yield (ΦPL=92%), high glass transition temperature (Tg=211°C) and high triplet energy (ET=2.85eV). In addition, the uniform amorphous thin film could be formed by spin-coating from its solution. These promising physical properties of the material made it suitable for using as UV–violet emitter in non-doped device and appropriate host in phosphorescent OLEDs. With SF-DPSO as an emitter, the non-doped solution processed device achieved an efficient UV–violet emission with the EL peak around 400nm. By using SF-DPSO as a host, solution processed blue and green phosphorescent organic light emitting diodes showed a high luminous efficiency of 13.7 and 30.2cd A−1, respectively.

Red emitting [Ir(C^N)2(N^N)]+complexes employing bidentate 2,2′:6′,2′′-terpyridine ligands for light-emitting electrochemical cells

2,2':6',2''-Terpyridine (tpy), 4'-(4-HOC6H4)-2,2':6',2''-terpyridine (1), 4'-(4-MeOC6H4)-2,2':6',2''-terpyridine (2), 4'-(4-MeSC6H4)-2,2':6',2''-terpyridine (3), 4'-(4-H2NC6H4)-2,2':6',2''-terpyridine (4) and 4'-(4-pyridyl)-2,2':6',2''-terpyridine (4) act as N^N chelates in complexes of the type [Ir(C^N)2(N^N)][PF6] in which the cyclometallating ligand, C^N, is derived from 2-phenylpyridine (Hppy) or 3,5-dimethyl-1-phenyl-1H-pyrazole (Hdmppz). The single crystal structures of eight complexes have been determined, and in each iridium(III) complex cation, the non-coordinated pyridine ring of the tpy unit is involved in a face-to-face π-stacking interaction with the cyclometallated ring of an adjacent ligand. Solution NMR spectra of the [Ir(ppy)2(N^N)](+) complexes are consistent with the presence of a non-classical hydrogen bond between the non-coordinated N-donor of the tpy domain and a CH unit of one pyridine ring of an adjacent ppy(-) ligand; the presence of the N···HC interaction was confirmed in one of the solid-state structures. The pendant pyridine ring of the coordinated tpy undergoes hindered rotation on the NMR timescale at 295 K. In CH2Cl2, the complexes are orange or red emitters, with λ(max)(em) in the range 580 to 642 nm; photoluminescence quantum yields (PLQY) are <10%, and lifetimes range from 54 to 136 ns. N-Methylation of the pendant 4'-(4-pyridyl) group in [Ir(dmppz)2(pytpy)][PF6] essentially quenches the emission. Light-emitting electrochemical cells (LECs) have been fabricated in a thin film configuration; the emission spectra of the LECs are red-shifted with respect to the PL spectra of the corresponding complex in thin film configuration. For the device incorporating [Ir(ppy)2(pytpy)][PF6], the PL to EL red-shift is extremely large and this is indicative of a different emitting state being involved. The most efficient devices used [Ir(ppy)2(1)][PF6], [Ir(ppy)2(2)][PF6] or [Ir(ppy)2(3)][PF6] in the emissive layer; the devices exhibited rapid turn-on times, but showed relatively low efficiencies in accordance with the solid state photoluminescence quantum yields.

Efficient energy transfer in a new hybrid diphenylfluorene derivative–CdS quantum dot nanocomposite

We report the synthesis of a novel compound, 9,9-bis(3′-aminopropyl)-2,7-diphenylfluorene (BAPDPF), and a new approach to graft the BAPDPF onto a CdS quantum dot (QD) surface via an acylation reaction. FT-IR and TGA characterizations indicate the formation of robust bonding between BAPDPF and QDs; the structures of the bare QDs and BAPDPF–CdS QD hybrid nanocomposites estimated by transmission electron microscopy (TEM) showed that they have the same size of about 3.5 nm. The extent of the spectral overlap between the emission of BAPDPF and absorption of QDs, and the change of fluorescence emission for the organic and inorganic components of the hybrid, demonstrate that the energy transfer process occurs from BAPDPF to the CdS QDs. The energy transfer of about 44% efficiency is corroborated by time-resolved fluorescence measurements, and then the solid-state photoluminescence quantum yield (PLQY) of the nanocomposite is measured using an integrating sphere and a conventional fluorimeter. Because of the fact that the PLQY of the nanocomposite is 9.1 times larger than that of the pristine QDs, due to the energy transfer between the donor and the acceptor and passivation effects on the surface of the acceptor, the presented BAPDPF–CdS QD hybrid nanocomposites are potentially interesting in nanoparticle-based light-emitting devices.

Thin film properties of triphenylamine-cored dendrimers: A molecular approach to control aggregation

The solid-state photophysical and charge transport properties of two first-generation dendrimers are presented. The dendrimers are comprised of a triphenylamine core, dendrons containing a phenyl branching unit with thiophene (Dendrimer 1) or bithiophene (Dendrimer 2) moieties, and dodecyl surface groups. For Dendrimer 1, the excited state is located within the center of the dendrimer giving rise to a moderate solid-state photoluminescence quantum yield (Φpl) (0.13) and significant charge trapping, with both observations due to the degree of overlap of the main electroactive chromophores on adjacent dendrimers. For Dendrimer 2, the excited state is located within the dendron and in the solid-state this leads to a strongly red-shifted and weakened emission (Φpl~0.02) due to strong intermolecular chromophore interactions. For films of Dendrimer 2 the charge mobility was higher than Dendrimer 1 but was still limited by a low density of strongly interacting electroactive chromophores. The pronounced difference between the solid-state properties of the two dendrimers is simply engineered by the addition of an extra thiophene in each of the dendrons.

Preparation, crystal structure, and solid-state optical property of a disulfonic acid/amine fluorescent complex composed of 4,4′-biphenyldisulfonic acid and 2-naphthylethylamine

Solid-state disulfonic acid/amine fluorescent host complexes including methanol (MeOH) as guests were successfully prepared using 4,4′-biphenyldisulfonic acid and 2-naphthylethylamine as component molecules. Although the crystal structure of the obtained host complex is similar to that of the corresponding dicarboxylic acid/amine host complex, the solid-state photo-luminescence quantum yield of the disulfonic acid/amine fluorescent host complex is increased relative to those of the corresponding dicarboxylic acid/amine host complex.