Stable room-temperature continuous-wave lasing in quasi-2D perovskite films.

Organic-inorganic lead halide quasi-two-dimensional (2D) perovskites are promising gain media for lasing applications because of their low cost, tunable colour, excellent stability and solution processability1-3. Optically pumped continuous-wave (CW) lasing is highly desired for practical applications in high-density integrated optoelectronics devices and constitutes a key step towards electrically pumped lasers4-6. However, CW lasing has not yet been realized at room temperature because of the 'lasing death' phenomenon (the abrupt termination of lasing under CW optical pumping), the cause of which remains unknown. Here we study lead halide-based quasi-2D perovskite films with different organic cations and observe that long-lived triplet excitons considerably impede population inversion during amplified spontaneous emission and optically pumped pulsed and CW lasing. Our results indicate that singlet-triplet exciton annihilation is a possible intrinsic mechanism causing lasing death. By using a distributed-feedback cavity with a high quality factor and applying triplet management strategies, we achieve stable green quasi-2D perovskite lasers under CW optical pumping in air at room temperature. We expect that our findings will pave the way to the realization of future current-injection perovskite lasers.

High performance from extraordinarily thick organic light-emitting diodes.

Organic light-emitting diode (OLED) technology is promising for applications in next-generation displays and lighting. However, it is difficult-especially in large-area mass production-to cover a large substrate uniformly with organic layers, and variations in thickness cause the formation of shunting paths between electrodes1,2, thereby lowering device production yield. To overcome this issue, thicker organic transport layers are desirable because they can cover particles and residue on substrates, but increasing their thickness increases the driving voltage because of the intrinsically low charge-carrier mobilities of organics. Chemical doping of organic layers increases their electrical conductivity and enables fabrication of thicker OLEDs3,4, but additional absorption bands originating from charge transfer appear5, reducing electroluminescence efficiency because of light absorption. Thick OLEDs made with organic single crystals have been demonstrated6, but are not practical for mass production. Therefore, an alternative method of fabricating thicker OLEDs is needed. Here we show that extraordinarily thick OLEDs can be fabricated by using the organic-inorganic perovskite methylammonium lead chloride, CH3NH3PbCl3 (MAPbCl3), instead of organics as the transport layers. Because MAPbCl3 films have high carrier mobilities and are transparent to visible light, we were able to increase the total thickness of MAPbCl3 transport layers to 2,000 nanometres-more than ten times the thickness of standard OLEDs-without requiring high voltage or reducing either internal electroluminescence quantum efficiency or operational durability. These findings will contribute towards a higher production yield of high-quality OLEDs, which may be used for other organic devices, such as lasers, solar cells, memory devices and sensors.

A Rigid Multiple Resonance Thermally Activated Delayed Fluorescence Core Toward Stable Electroluminescence and Lasing.

The investigation of organic light-emitting diodes (OLEDs) and organic laser devices with thermally activated delayed fluorescence (TADF) molecules is emerging due to the potential of harnessing triplets. In this work, a boron/nitrogen multiple-resonance TADF polycyclic framework fusing carbazole units (CzBNPh) was proposed. CzBNPh exhibited a narrowband emission (<30 nm), a unity photoluminescence quantum yield, and a fast radiative rate. Consequently, CzBNPh demonstrated a low distributed feedback (DFB) lasing threshold of 0.68 µJ cm-2 . Furthermore, the stimulated emission zone of CzBNPh was effectively separated from its singlet and triplet absorption, thereby minimizing the singlet-triplet annihilation under long-pulsed excitation ranging from 20 µs to 2.5 ms. Significantly, the enhanced rigid molecular conformation, thermal stability, and photo-stability resulted in improved lasing and electroluminescence stability compared to that of 5,9-diphenyl-5,9-diaza-13b-boranaphtho[3,2,1-de]anthracene (DABNA)-core. These findings indicate the potential of CzBN-core as a promising framework for achieving long-pulsed wave and electrically-pumped lasing in the future.

Enhanced Operational Durability of Thermally Activated Delayed Fluorescence-Based Organic Light-Emitting Diodes with a Triazine Electron Transporter.

In organic light-emitting diodes (OLEDs) based on materials that show thermally activated delayed fluorescence (TADF), the internal quantum efficiency of 100 % can be obtained without using phosphorescence-based organometallics that contain rare metals. Therefore, with TADF-based emitters, it is possible to fabricate high-performing OLEDs at a lower cost. However, compared with fluorescence- and phosphorescence-based OLEDs, an understanding of degradation mechanisms in TADF-based OLEDs is still insufficient for future commercialization. In particular, it is widely recognized that the development of electron transport materials is crucial for improving OLED characteristics, especially driving voltages and operational durability. In this study, it was demonstrated that the operational durability of TADF-based OLEDs was greatly improved by introducing a triazine-based material of 2,4,6-tris(1,1'-biphenyl-4-yl)-[1,3,5]triazine (pT2T) as a hole-blocking layer (HBL) compared with a conventional HBL material of 2,4,6-tris(biphenyl-3-yl)-[1,3,5]triazine (T2T). Several experiments were carried out to make the reasons of the improved durability clearer, and attributed the improved durability to the shift of a carrier recombination zone from the emitting layer/HBL interface and the suppressed formation of excited-state quenchers in the pT2T HBL, because of the higher electron mobility of pT2T and the better stability of its radical anion state.

Progress and Perspective toward Continuous-Wave Organic Solid-State Lasers.

A continuous-wave (CW) organic solid-state laser is highly desirable for spectroscopy, sensing, and communications, but is a significant challenge in optoelectronics. The accumulation of long-lived triplet excitons and relevant excited-state absorptions, as well as singlet-triplet annihilation, are the main obstacles to CW lasing. Here, progress in singlet- and triplet-state utilizations in organic gain media is reviewed to reveal the issues in working with triplets. Then, exciton behaviors that inhibit light oscillations during long excitation pulses are discussed. Further, recent advances in increasing organic lasing pulse widths from microseconds toward the indication of CW operation are summarized with respect to molecular designs, advanced resonator architectures, triplet scavenging, and potential triplet contribution strategies. Finally, future directions and perspectives are proposed for achieving stable CW organic lasers with significant triplet contribution.

Functionalization of diameter-sorted semiconductive SWCNTs with photosensitizing porphyrins: syntheses and photoinduced electron transfer.

Covalent functionalization of diameter sorted SWCNTs with porphyrins (MP), and photochemistry to establish nanotube diameter-dependent charge separation efficiencies are reported. The MP-SWCNT(n,m) [M=2H or Zn, and (n,m)=(7,6) or (6,5)] nanohybrids are characterized by a variety of spectroscopic, thermogravimetric, TEM imaging techniques, and also by DFT MO calculations. The thermogravimetric, Raman and fluorescence studies reveal the presence of a moderate number of porphyrins on the SWCNT surface. The MO results suggest charge separation (CS) via the excited state of MP. Time-resolved fluorescence studies reveal quenching of the singlet excited state of the MP with SWCNT(n,m), giving the rate constants of charge separation (k(CS)) in the range of (4-5)×10(9) s(-1). Nanosecond transient absorption measurements confirm the charge-separated radical cation and the radical anion as [MP(.+)-SWCNT(.-)] with their characteristic absorption bands in the visible and near-IR regions. The charge separated states persist for about 70-100 ns thus giving an opportunity to utilize them to build photoelectrochemical cells, which allowed us to derive the structure-reactivity relationship between the nature of porphyrin and diameter of the employed nanotubes.

Photoinduced charge separation in three-layer supramolecular nanohybrids: fullerene-porphyrin-SWCNT.

Photoinduced charge separation processes of three-layer supramolecular hybrids, fullerene-porphyrin-SWCNT, which are constructed from semiconducting (7,6)- and (6,5)-enriched SWCNTs and self-assembled via π-π interacting long alkyl chain substituted porphyrins (tetrakis(4-dodecyloxyphenyl)porphyrins; abbreviated as MP(alkyl)(4)) (M = Zn and H(2)), to which imidazole functionalized fullerene[60] (C(60)Im) is coordinated, have been investigated in organic solvents. The intermolecular alkyl-π and π-π interactions between the MP(alkyl)(4) and SWCNTs, in addition, coordination between C(60)Im and Zn ion in the porphyrin cavity are visualized using DFT calculations at the B3LYP/3-21G(*) level, predicting donor-acceptor interactions between them in the ground and excited states. The donor-acceptor nanohybrids thus formed are characterized by TEM imaging, steady-state absorption and fluorescence spectra. The time-resolved fluorescence studies of MP(alkyl)(4) in two-layered nanohybrids (MP(alkyl)(4)/SWCNT) revealed efficient quenching of the singlet excited states of MP(alkyl)(4) ((1)MP*(alkyl)(4)) with the rate constants of charge separation (k(CS)) in the range of (1-9) × 10(9) s(-1). A nanosecond transient absorption technique confirmed the electron transfer products, MP˙(+)(alkyl)(4)/SWCNT˙(-) and/or MP˙(-)(alkyl)(4)/SWCNT˙(+) for the two-layer nanohybrids. Upon further coordination of C(60)Im to ZnP, acceleration of charge separation via(1)ZnP* in C(60)Im→ZnP(alkyl)(4)/SWCNT is observed to form C(60)˙(-)Im→ZnP˙(+)(alkyl)(4)/SWCNT and C(60)˙(-)Im→ZnP(alkyl)(4)/SWCNT˙(+) charge separated states as supported by the transient absorption spectra. These characteristic absorptions decay with rate constants due to charge recombination (k(CR)) in the range of (6-10) × 10(6) s(-1), corresponding to the lifetimes of the radical ion-pairs of 100-170 ns. The electron transfer in the nanohybrids has further been utilized for light-to-electricity conversion by the construction of proof-of-concept photoelectrochemical solar cells.

Numerical Study of Triplet Dynamics in Organic Semiconductors Aimed for the Active Utilization of Triplets by TADF under Continuous-Wave Lasing.

The limitation of lasing duration less than nanosecond order has been a major problem for realizing organic solid-state continues-wave (CW) lasers and organic semiconductor laser diodes. Triplets accumulation under CW excitation has been well recognized as a critical inhibiting factor. To overcome this issue, the utilization of thermally activated delayed fluorescence (TADF) emitters is a promising mechanism because of efficient reverse intersystem crossing. Herein, we model the triplet accumulation processes under lasing and propose the active utilization of TADF for lasing based on our simulation analysis. We used the rate constants experimentally determined from the optical properties of a boron difluoride curcuminoid fluorophore showing both TADF and lasing. We demonstrate that the intersystem crossing efficiency is gradually increased after the convergence of relaxation oscillation, i.e., terminating laser oscillation. In addition, we found that when the reverse intersystem crossing rate is close to the intersystem crossing rate, CW lasing becomes dominant.

Bionano donor-acceptor hybrids of porphyrin, ssDNA, and semiconductive single-wall carbon nanotubes for electron transfer via porphyrin excitation.

Photoinduced electron transfer in self-assemblies of porphyrins ion-paired with ssDNA wrapped around single-wall carbon nanotubes (SWCNTs) has been reported. To accomplish the three-component hybrids, two kinds of diameter-sorted semiconducting SWCNT(n,m)s of different diameter ((n,m) = (6,5) and (7,6)) and free-base or zinc porphyrin bearing peripheral positive charges ((TMPyP(+))M (tetrakis(4-N-methylpyridyl)porphyrin); M = Zn and H(2)) serving as light-absorbing photoactive materials are utilized. The donor-acceptor hybrids are held by ion-pairing between the negatively charged phosphate groups of ssDNA on the surface of the SWCNT and the positively charged at the ring periphery porphyrin macrocycle. The newly assembled bionano donor-acceptor hybrids have been characterized by transmission electron microscopy (TEM) and spectroscopic methods. Photoinduced electron transfer from the excited singlet porphyrin to the SWCNTs directly and/or via ssDNA as an electron mediator has been established by performing systematic studies involving the steady-state and time-resolved emission as well as the transient absorption studies. Higher charge-separation efficiency has been successfully demonstrated by the selection of the appropriate semiconductive SWCNTs with the right band gap, in addition to the aid of ssDNA as the electron mediator.

Diameter-sorted SWCNT-porphyrin and SWCNT-phthalocyanine conjugates for light-energy harvesting.

A non-covalent double-decker binding strategy is employed to construct functional supramolecular single-wall carbon nanotubes (SWCNT)-tetrapyrrole hybrids capable of undergoing photoinduced electron transfer and performing direct conversion of light into electricity. To accomplish this, two semiconducting SWCNTs of different diameters (6,5 and 7,6) were modified via π-π stacking of pyrene functionalized with an alkyl ammonium cation (PyrNH(3)(+)). Such modified nanotubes were subsequently assembled via dipole-cation binding of zinc porphyrin with one (1) or four benzo-18-crown-6 cavities (2) or phthalocyanine with four benzo-18-crown-6 cavities at the ring periphery (3), employed as visible-light photosensitizers. Upon charactering the conjugates using TEM and optical techniques, electron transfer via photoexcited zinc porphyrin and phthalocyanine was investigated using time-resolved emission and transient absorption techniques. Higher charge-separation efficiency is established for SWCNT(7,6) with a narrow band gap than the thin SWCNT(6,5) with a wide band gap. Photoelectrochemical studies using FTO/SnO(2) electrodes modified with these donor-acceptor conjugates unanimously demonstrated the ability of these conjugates to convert light energy into electricity. The photocurrent generation followed the trend observed for charge separation, that is, incident-photon-to-current efficiency (IPCE) of a maximum of 12 % is achieved for photocells with FTO/SnO(2)/SWCNT(7,6)/PyrNH(3)(+):1.

Fullerene- and pyromellitdiimide-appended tripodal ligands embedded in light-harvesting porphyrin macrorings.

Three new tripyridyl tripodal ligands appended with either fullerene or pyromellitdiimide moieties, named C(60)-s-Tripod, C(60)-l-Tripod, and PI-Tripod, were synthesized and introduced into a porphyrin macroring N-(1-Zn)(3) (where 1-Zn = trisporphyrinatozinc(II)). From UV-vis absorption and fluorescence titration data, the binding constants of C(60)-s-Tripod, C(60)-l-Tripod, and PI-Tripod with N-(1-Zn)(3) in benzonitrile were estimated to be 3 × 10(8), 1 × 10(7), and 2 × 10(7) M(-1), respectively. These large binding constants denote multiple interactions of the ligands to N-(1-Zn)(3). The binding constants of the longer ligand (C(60)-l-Tripod) and the pyromellitdiimide ligand (PI-Tripod) are almost the same as those without the fullerene or pyromellitdiimide groups, indicating that they interact via three pyridyl groups to the porphyrinatozinc(II) coordination. In contrast, the larger binding constants and the almost complete fluorescence quenching in the case of the shorter ligand (C(60)-s-Tripod) indicate that the interaction with N-(1-Zn)(3) is via two pyridyl groups to the porphyrinatozinc(II) coordination and a π-π interaction of the fullerene to the porphyrin(s). The fluorescence of N-(1-Zn)(3) was quenched by up to 80% by the interaction of C(60)-l-Tripod. The nanosecond transient absorption spectra showed only the excited triplet peak of the fullerene on selective excitation of the macrocyclic porphyrins, indicating that energy transfer from the excited N-(1-Zn)(3) group to the fullerenyl moiety occurs in the C(60)-l-Tripod/N-(1-Zn)(3) composite. In the case of PI-Tripod, the fluorescence of N-(1-Zn)(3) was quenched by 45%. It seems that the fluorescence quenching probably originates from electron transfer from the excited N-(1-Zn)(3) group to the pyromellitdiimide moiety.

Sequential charge separation in two axially linked phenothiazine-aluminum(III) porphyrin-fullerene triads.

New supramolecular triads (PTZpy→AlPor-C(60), TPTZpy→AlPor-C(60)), containing aluminum(III) porphyrin (AlPor), fullerene (C(60)), and phenothiazine (phenothiazine = PTZ, 2-methylthiophenothaizine = TPTZ) have been constructed. In these triads the fullerene and phenothiazine units are bound axially to opposite faces of the porphyrin plane via covalent and coordination bonds, respectively. The ground- and excited-state properties of the triads and reference dyads are studied using steady-state and time-resolved spectroscopic techniques. The time-resolved data show that photoexcitation results in charge separation from the excited singlet state of the porphyrin to the C(60) unit, generating (Donor)py→AlPor(•+)-C(60)(•-), Donor = PTZ and TPTZ. A subsequent hole shift from the porphyrin to phenothiazine generates the charge-separated state (Donor)(•+)py→AlPor-C(60)(•-). The lifetime of the charge separation exhibits a modest increase from 39 ns in the absence of the donor to 100 ns in PTZpy→AlPor-C(60) and 83 ns in TPTZpy→AlPor-C(60). These lifetimes are discussed in terms of the electronic coupling between phenothiazine, the porphyrin, and C(60).

Fabrication of ZnPc/protein nanohorns for double photodynamic and hyperthermic cancer phototherapy.

Multifunctionalization of carbon nanotubules is easily achieved by attaching functional molecules that provide specific advantages for microscopic applications. We fabricated a double photodynamic therapy (PDT) and photohyperthermia (PHT) cancer phototherapy system that uses a single laser. Zinc phthalocyanine (ZnPc) was loaded onto single-wall carbon nanohorns with holes opened (SWNHox), and the protein bovine serum albumin (BSA) was attached to the carboxyl groups of SWNHox. In this system, ZnPc was the PDT agent, SWNHox was the PHT agent, and BSA enhanced biocompatibility. The double phototherapy effect was confirmed in vitro and in vivo. When ZnPc-SWNHox-BSA was injected into tumors that were subcutaneously transplanted into mice, the tumors almost disappeared upon 670-nm laser irradiation. In contrast, the tumors continued to grow when only ZnPc or SWNHox-BSA was injected. We conclude that carbon nanotubules may be a valuable new tool for use in cancer phototherapy.

Sensitive efficiency of photoinduced electron transfer to band gaps of semiconductive single-walled carbon nanotubes with supramolecularly attached zinc porphyrin bearing pyrene glues.

Photoinduced electron transfer in self-assembled single-walled carbon nanotube (SWNT)/zinc porphyrin (ZnP) hybrids utilizing (7,6)- and (6,5)-enriched SWNTs has been investigated. Toward this, first, zinc porphyrin was covalently functionalized to possess four pyrene entities (ZnP(pyr)(4)). Exfoliation of the semiconducting nanotube bundles occurred due to pi-pi-type interactions with the pyrene and porphyrin entities in organic solvents. The nanohybrids thus formed were isolated and characterized by TEM, UV-visible-near-IR, and Raman spectroscopy. Free-energy calculations suggested the possibility of electron transfer in both the (7,6)- and (6,5)-possessing ZnP(pyr)(4)/SWNT nanohybrids. Accordingly, fluorescence studies revealed efficient quenching of the singlet excited state of ZnP in the nanohybrids, originating from the charge separation, as confirmed by observation of a ZnP pi-cation radical in transient absorption spectra. The rates of charge separation were found to be slightly higher for (7,6)-SWNT-derived hybrids compared to the (6,5)-SWNT-derived hybrids. Charge recombination revealed an opposite effect, indicating that the (7,6)-SWNTs are slightly better for charge stabilization compared to the (6,5)-SWNTs. The present nanohybrids were further utilized to photochemically reduce the hexyl viologen dication in the presence of a sacrificial electron donor in an electron-pooling experiment, offering additional proof for the occurrence of photoinduced charge separation and potential utilization of these materials in light-energy-harvesting applications. Finally, solar cells constructed using the ZnP/SWNT hybrids revealed higher efficiency for the ZnP(pyr)(4)/(7,6)-SWNT hybrid with narrower nanotube band gap compared with the ZnP(pyr)(4)/(6,5)-SWNT having a relatively wider band gap.

A carbon nanohorn-porphyrin supramolecular assembly for photoinduced electron-transfer processes.

A supramolecular assembly of zinc porphyrin-carbon nanohorns (CNHs) was constructed in a polar solvent. An ammonium cation was covalently connected to the CNH through a spacer (sp) (CNH-sp-NH(3)(+)) and bound to a crown ether linked to a zinc porphyrin (Crown-ZnP). Nanohybrids CNH-sp-NH(3)(+);Crown-ZnP and CNH-sp-NH(3)(+) were characterized by several techniques, such as high-resolution transmission electron microscopy, thermogravimetric analysis, X-ray photoelectron spectroscopy, and Raman spectroscopy. The photoinduced electron-transfer processes of the nanohybrids have been confirmed by using time-resolved absorption and fluorescence measurements by combining the steady-state spectral data. Fluorescence quenching of the ZnP unit by CNH-sp-NH(3)(+) has been observed, therefore, photoinduced charge separation through the excited singlet state of the ZnP unit is suggested for the hybrid material, CNH-sp-NH(3)(+);Crown-ZnP. As transient absorption spectral experiments reveal the formation of the radical cation of the ZnP unit, electron generation is suggested as a counterpart of the charge-separation on the CNHs; such an electron on the CNHs is further confirmed by migrating to the hexylviologen dication (HV(2+)). Accumulation of the electron captured from HV(*+) is observed as electron pooling in solution in the presence of a hole-shifting reagent. Photovoltaic performance with moderate efficiency is confirmed for CNH-sp-NH(3)(+);Crown-ZnP deposited onto nanostructured SnO(2) films.

Axle length effect on photoinduced electron transfer in triad rotaxane with porphyrin, [60]fullerene, and triphenylamine.

Photoinduced multiple electron-transfer processes of a newly synthesized rotaxane with one acceptor and two donors are studied with the time-resolved fluorescence and absorption methods. In this rotaxane, zinc porphyrin (ZnP) with a crown-ether necklace is employed as a photosensitized electron donor; through the crown-ether, a short axle with C(60) and triphenylamine (TPA) at both terminals is penetrating as an electron acceptor and a hole-shift, respectively (abbreviated as (ZnP;C(60)-(A(S))-TPA)(Rot)). The time-resolved fluorescence and transient absorption measurements reveal that the through-space electron-transfer processes take place via the excited states of the ZnP unit to the spatially arranged C(60) moiety, giving the radical ion pair (ZnP(*+);C(60)(*-)-(A(S))-TPA)(Rot) in polar solvents. Consecutively, (ZnP;C(60)(*-)-(A(S))-TPA(*+))(Rot) is also generated by the through-space hole-shift between ZnP and TPA, in addition to the through-bond charge separation via the excited state of the C(60) moiety. Both radial ion pairs have lifetimes of 320-420 ns, which are longer than those of the previously reported similar rotaxane with cationic longer axle (150-170 ns).

Photochemical charge separation in supramolecular phthalocyanine-multifullerene conjugates assembled by crown ether-alkyl ammonium cation interactions.

Self-assembled phthalocyanine-multifullerene donor-acceptor conjugates have been formed by crown ether-ammonium cation dipole-ion binding strategy to probe the photochemical charge separation. To achieve this, phthalocyanine is functionalized to possess four 18-crown-6 moieties on the macrocycle periphery, whereas fullerene is functionalized to possess an alkyl ammonium cation of short and long chain lengths. Stable donor-acceptor conjugates accommodating multifullerene entities have been obtained by the crown ether-ammonium cation inclusion complexation. From the efficient fluorescence quenching of the zinc phthalocyanine by the bound fullerene entities, the rate constants of charge separation are evaluated to be slightly larger for closely held via shorter alkyl chain length fullerene, which are also larger compared to the earlier reported analogous zinc porphyrin-multifullerene conjugate. Nanosecond transient absorption studies yielded spectral signatures corresponding to both the phthalocyanine radical cation and fullerene radical anion at the same time, providing evidence of light-induced electron transfer within the conjugates. The evaluated lifetimes of the radical ion pairs in the present phthalocyanine-fullerene conjugates are found to be hundreds of nanoseconds and are much longer compared to the earlier reported conjugate of zinc porphyrin analogue, revealing higher possible usage of the generated radical ion pairs.

Suppression of external quantum efficiency rolloff in organic light emitting diodes by scavenging triplet excitons.

Large external quantum efficiency rolloff at high current densities in organic light-emitting diodes (OLEDs) is frequently caused by the quenching of radiative singlet excitons by long-lived triplet excitons [singlet-triplet annihilation (STA)]. In this study, we adopted a triplet scavenging strategy to overcome the aforementioned STA issue. To construct a model system for the triplet scavenging, we selected 2,6-dicyano-1,1-diphenyl-λ5σ4-phosphinine (DCNP) as the emitter and 4,4'-bis[(N-carbazole)styryl]biphenyl (BSBCz) as the host material by considering their singlet and triplet energy levels. In this system, the DCNP's triplets are effectively scavenged by BSBCz while the DCNP's singlets are intact, resulting in the suppressed STA under electrical excitation. Therefore, OLEDs with a 1 wt.%-DCNP-doped BSBCz emitting layer demonstrated the greatly suppressed efficiency rolloff even at higher current densities. This finding favourably provides the advanced light-emitting performance for OLEDs and organic semiconductor laser diodes from the aspect of the suppressed efficiency rolloff.

Photoinduced electron transfer in zinc phthalocyanine loaded on single-walled carbon nanohorns in aqueous solution.

Notable electronic communication within ZnPc-SWNHox nanoensembles, where ZnPc is zinc phthalocyanine and SWNHox is an oxidized single-walled nanohorn, in both the ground and excited states is revealed by steady-state absorption and fluorescence spectroscopy measurements. The details of electron transfer reported here with time-resolved absorption and fluorescence measurements may broaden the use of SWNHox nanoensembles in photochemistry and photobiology.

Energy transfer followed by electron transfer in a porphyrin macrocycle and central acceptor ligand: a model for a photosynthetic composite of the light-harvesting complex and reaction center.

A system that models a photosynthetic composite of the light-harvesting complex and reaction center is reported in which light energy collected by cyclic antenna porphyrins is transferred to a central energy-acceptor porphyrin, followed by photoinduced electron transfer to a fullerene positioned above the ring plane. Pyridyl tripodal ligands appended with bis(phenylethynyl)porphyrinatozinc(II) (ZnP-Tripod) and additional fulleropyrrolidine moieties (C(60)-ZnP-Tripod) were synthesized as the reaction center units. The tripodal ligand was strongly accommodated by the light-harvesting porphyrin macrocycle N-(1-Zn)(3) (1-Zn = trisporphyrinatozinc(II)) by using three-point coordination of pyridyl to uncoordinated porphyrinatozinc sites to afford a stable 1:1 composite. The binding constants for ZnP-Tripod and C(60)-ZnP-Tripod in benzonitrile were estimated from steady-state fluorescence titrations to be 1.4x10(7) and 1.6x10(7) M(-1), respectively. The steady-state fluorescence titration, fluorescence lifetime, and transient absorption studies revealed that in both composites the excitation energy collected by the nine porphyrins of N-(1-Zn)(3) was efficiently transferred to a ZnP moiety by means of a through-space mechanism with a quantum yield of approximately 90%. Furthermore, in the composite with C(60)-ZnP-Tripod, the converged energy at the ZnP moiety induced electron transfer to the C(60) moiety, which afforded the stable charge-separated state (Phi(CS)>90%).