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Four new donor-acceptor-acceptor' (D-A-A')-configured donors, CPNT, DCPNT, CPNBT, and DCPNBT equipped with naphtho[1,2-c:5,6-c']bis([1,2,5]-thiadiazole) (NT) or naphtho[2,3-c][1,2,5]thiadiazole (NBT) as the central acceptor (A) unit bridging triarylamine donor (D) and cyano or dicyanovinylene acceptor (A'), were synthesized and characterized. All molecules exhibit bathochromic absorption shifts as compared to those of the benzothiadiazole (BT)-based analogues owing to improved electron-withdrawing and quinoidal character of NT and NBT cores that lead to stronger intramolecular charge transfer. Favorable energy level alignments with C70 , together with the good thermal stability and the antiparallel dimeric packing render CPNT and DCPNT suitable donors for vacuum-processed organic photovoltaics (OPV)s. OPVs based on DCPNT : C70 active layers displayed the best power conversion efficiency (PCE)=8.3%, along with an open circuit voltage of 0.92 V, a short circuit current of 14.5 mA cm-2 and a fill factor of 62% under 1 sun intensity, simulated AM1.5G illumination. Importantly, continuous light-soaking with AM 1.5G illumination has verified the durability of the devices based on CPNT:C70 and DCPNT : C70 as the active blends. The devices were examined for their feasibility of indoor light harvesting under 500 lux illumination by a TLD-840 fluorescent lamp, giving PCE=12.8% and 12.6%, respectively. These results indicate that the NT-based D-A-A'-type donors CPNT and DCPNT are potential candidates for high-stability vacuum-processed OPVs suitable for indoor energy harvesting.

Herein, core-twisted tetrachloroperylenediimides (ClPDIs) were introduced as new efficient electron-transporting materials (ETMs) to replace the commonly used fullerene acceptor PC61 BM in inverted planar perovskite solar cells (PSCs). ClPDI showed a low-lying lowest unoccupied molecular orbital (LUMO) energy level of -3.95 eV, which was compatible with the conduction band of CH3 NH3 PbI3-x Clx (-3.90 eV). In addition, the role of the length of the alkyl side chain at the imide position of ClPDI in modulating the molecular solubility, aggregation capacity for charge-transport properties, surface hydrophobicity, and PSC performance was investigated. The device based on ClPDI-C4 (ClPDI with n-butyl side chains) as ETM achieved a maximum power conversion efficiency (PCE) of 17.3 % under standard AM 1.5G illumination, which iwas very competitive with that of the reference device employing PC61 BM/C60 (PCE=17.2 %) as ETM. Moreover, the devices with ClPDIs as ETMs exhibited better device stability than that with PC61 BM/C60 . This work highlights the great potential of ClPDI derivatives as low-cost (≈2.0 USD g-1 ) and effective ETMs to obtain efficient solution-processed inverted PSCs. This class of ClPDI derivatives is expected further promote the performance and stability of PSCs after extended investigation.

An acceptor-donor-acceptor (A-D-A)-type non-fullerene acceptor (NFA), PTTtID-Cl, featuring thieno[3,2-b]thieno[2''',3''':4'',5'']-pyrrolo[2'',3'':4',5']thieno[2',3':4,5]thieno-[2,3-d]pyrrole (DTPTt) as the electron-rich core and 2-(5,6-dichloro-3-oxo-2,3-dihydro-1H-inden-1-ylidene)malononitrile (ID-Cl) as the peripheral electron-deficient terminal group was synthesized and characterized. PTTtID-Cl exhibited strong absorption in the range of 700-850 nm in CHCl3 and redshifted absorption centered at 881 nm in a thin film. The near infrared (NIR)-absorption of PTTtID-Cl was combined with a low-bandgap polymer donor (PTB7-Th) to achieve binary and semitransparent organic photovoltaics (OPVs) with a power conversion efficiency (PCE) of 8.9 % and 7.7 % (with an average visible transmittance (AVT) of 16.7 %), respectively. A ternary device with a ratio of PM7/PTTtID-Cl/IT-4F=1:0.15:0.85 (w/w) achieved a short-circuit current density of 19.46 mA cm-2 , an open-circuit voltage of 0.87 V, and a fill factor of 71.2 %, giving a PCE of 12.0 %. In addition, by employing the Ag/ITO/Ag microcavity structure, semitransparent colorful binary organic photovoltaics (OPVs) with superior transparency of 27.9 % at 427 nm and 22.7 % at 536 nm for blue and green devices, respectively, were prepared. The semitransparent colorful devices based on the optimized ternary blend gave PCEs of 8.7 %, 8.4 %, and 9.1 % for blue, green, and red devices, respectively. These results indicate the promising potential of PTTtID-Cl as a NIR-absorption NFA for applications in semitransparent colorful binary and ternary OPVs.

A series of twisted N,N-linked benzo[ghi]-perylenetriimide dimers (t-BPTI) with various lengths of the α-branched alkyl side chain at the six-membered imide ring position was designed, synthesized, and characterized. These compounds showed the low-lying LUMO energy level of -3.78 eV, which was similar to that of PC61 BM (-3.71 eV), but with intensive optical absorption in the range 350-500 nm. The twisted molecular geometry with two nearly perpendicular BPTI planes achieved a favorable nanoscale phase separation by relieving the self-aggregation of rigid BPTI units in blend films. The acceptor t-BPTI-3 unit with the longest alkyl side chains has been demonstrated to be an efficient electron acceptor in solution-processed bulk heterojunction organic photovoltaics (OPV), giving a power conversion efficiency of 3.68 % when using conjugated polymer PTB7-Th as the donor and without additional treatments.

A heterobimetallic corrole complex, comprising oxygen reduction reaction (ORR) active non-precious metals Co and Fe with a corrole-N4 center (PhFCC), is successfully synthesized and used to prepare a dual-atom molecular catalyst (DAMC) through subsequent low-temperature pyrolysis. This low-temperature pyrolyzed electrocatalyst exhibited impressive ORR performance, with onset potentials of 0.86 and 0.94 V, and half-wave potentials of 0.75 and 0.85 V, under acidic and basic conditions, respectively. During potential cycling, this DAMC displayed half-wave potential losses of only 25 and 5 mV under acidic and alkaline conditions after 3000 cycles, respectively, demonstrating its excellent stability. Single-cell Nafion-based proton exchange membrane fuel cell performance using this DAMC as the cathode catalyst showed a maximum power density of 225 mW cm-2 , almost close to that of most metal-N4 macrocycle-based catalysts. The present study showed that preservation of the defined CoN4 structure along with the cocatalytic Fe-Cx site synergistically acted as a dual ORR active center to boost overall ORR performance. The development of DAMC from a heterobimetallic CoN4-macrocyclic system using low-temperature pyrolysis is also advantageous for practical applications.

Dilute donor organic solar cells (OSCs) are a promising technology to circumvent the trade‐off between open‐circuit voltage (Voc) and short‐circuit current density (Jsc). The origin of hole transport in OSCs with donor concentrations below the percolation threshold is diversely discussed in the community. Herein, both hole back transfer and long‐range hopping (tunneling) are analyzed as possible mechanisms of photocurrent in small molecule dilute donor OSCs using kinetic Monte Carlo (kMC) simulations. In contrast to previous kMC studies, the driving force for exciton dissociation is accounted for. As a study system, nitrogen‐bridged terthiophene (NBTT) molecules in a [6,6]‐phenyl‐C70‐butyric acid methyl ester (PC71BM) matrix are investigated. The simulations show that hole back transfer from the small molecule donor to the fullerene matrix explains the measured concentration dependences of the photocurrents as well as the Jsc dependence on the light intensity for donor concentrations below 5 wt%. For 5 wt%, distances between NBTT molecules decrease to reasonable ranges that long‐range hopping or tunneling cannot be discounted. Compared with polymer donors, larger hole localization is observed. The results emphasize that the barrier for hole back transfer is not only due to the highest occupied molecular orbital (HOMO) offset, but also by hole localization.

A series of twisted D–π–A type emitters based on the acridine donor unit and CN-substituted pyridine, pyrimidine, and benzene acceptor units are studied. They not only allow one to systematically probe the influence of different acceptor strengths, but also permit one to intriguingly probe the influence of tunable conformations (twist angles) within the acceptor moieties through controlling the orientation of asymmetric heteroaromatic ring relative to the donor component. Intramolecular charge-transfer transitions are observed in all these compounds and emission wavelengths are widely tunable from deep blue to yellow not only by the general acceptor strength due to the characters of heteroarene and CN-substitution pattern but also by the subtle control of in-acceptor conformation (twist angles). Small triplet-to-singlet energy gaps (ΔEST) and significant thermally activated delayed fluorescence (TADF) characteristics are obtained in a series of D–π–A compounds with sufficient acceptor strengths and tunable in-acceptor conformation, yielding a series of efficient blue-green to yellow TADF emitters with promisingly high photoluminescence quantum yields of 90%–100%. Highly efficient blue-green to yellow TADF organic light-emitting diodes (OLEDs) having external quantum efficiencies of up to 23.1%–31.3% are achieved using these efficient TADF emitters, which are among the most efficient TADF OLEDs ever reported.

Donor-acceptor-acceptor' small-molecule donors are synthesized to investigate regioisomeric effects on organic photovoltaic device performance. Cross-conjugation in 2-((7-(N-(2-ethylhexyl)-benzothieno[3,2-b]thieno[3,2-d]pyrrol-2-yl)benzo[c][1,2,5]thiadiazol-4-yl)methylene)malononitrile leads to an increased open-circuit voltage compared with its isomer 2-((7-(N-(2-ethylhexyl)-benzothieno[3,2-b]thieno[2,3-d]pyrrol-2-yl)benzo[c][1,2,5]thiadiazol-4-yl)methylene)malononitrile. A correlation is then established between molecular conjugation length and orbital energies, and hence open-circuit voltage.

The exciplex forming co-host with phosphorescent dopant system has potential to realize highly efficient phosphorescent organic light emitting didoes (PhOLEDs). However, the exciplex forming co-host for blue phosphorescent OLEDs has been rarely introduced because of higher triplet level of the blue dopant than green and red dopants. In this work, a novel exciplex forming co-host with high triplet energy level is developed by mixing a phosphine oxide based electron transporting material, PO-T2T, and a hole transporting material, N,N′-dicarbazolyl-3,5-benzene (mCP). Photo-physical analysis shows that the exciplexes are formed efficiently in the host and the energy transfer from the exciplex to blue phosphorescent dopant (iridium(III)bis[(4,6-difluorophenyl)-pyridinato-N,C2′]picolinate; FIrpic) is also efficient, enabling the triplet harvest without energy loss. As a result, an unprecedented high performance blue PhOLED with the exciplex forming co-host is demonstrated, showing a maximum external quantum efficiency (EQE) of 30.3%, a maximum power efficiency of 66 lm W−1, and low driving voltage of 2.75 at 100 cd m−2, 3.29 V at 1000 cd m−2, and 4.65 V at 10 000 cd m−2, respectively. The importance of the exciton confinement in the exciplex forming co-host is further investigated which is directly related to the performance of PhOLEDs.

Two bipolar hosts, CzDPO and CzDOxa, comprising a hole-transporting carbazole and an electron-transporting diphenyl phosphine oxide or oxadiazole with a saturated linker (9,10-dihydroanthracene) have been synthesized and characterized. The saturated linker limited the effective extension of π conjugation, leading to high triplet energies (ET=2.97–2.98 eV). The diastereomers with a rigid configuration provided an amorphous thin film with high thermal (Td=415–444 °C) and morphological stability (Tg=188–224 °C). The high triplet energies and bipolar carrier transport characteristics (ambipolariy) of CzDPO and CzDOxa can facilitate exothermic energy transfer to the dopants and balance carrier injection/transport in the emission layers. As a result, they were utilized as universal hosts for various phosphorescent OLEDs (from blue to red), showing average external quantum efficiencies (ηext=8.2–13.1 %) and low efficiency roll-off. In addition, we also fabricated dual-emitter white organic light-emitting diodes with a co-doped single emissive layer. WOLED hosted by CzDOxa exhibited satisfactory device efficiencies (14.4 %, 25.7 cd A−1, 27 lm W−1) with highly stable chromaticity (CIEx=0.26–0.28 and CIEy=0.38) at brightnesses from 560 to 15200 cd m−2.

Four new molecules with a donor-acceptor-acceptor (D-A-A) configuration, in which 2,1,3-benzoxadiazole or 2,1,3-benzoselenodiazole were adopted as the central bridging acceptor, were synthesized as electron donors for small-molecule organic solar cells. In conjunction with two previously reported 2,1,3-benzothiadiazole-based compounds, the influences of the benzochalcogenodiazole acceptor unit and the ditolylarylamine donor moiety on the molecular structure, electrochemical behavior, and optical properties of the materials were investigated systematically to obtain a clear structure-property relationship. Vacuum-deposited hybrid planar mixed-heterojunction devices fabricated with the new donors and C70 as the acceptor showed power conversion efficiencies in the range of 2.9-4.3 % under 1 sun (100 mW cm(-2) ) AM 1.5 G simulated solar illumination. The current density-voltage characteristics of solar cells at various light intensities were measured, which revealed a high bimolecular recombination.

Two new molecules, CzFCBI and CzFNBI, have been tailor-made to serve as bipolar host materials to realize high-efficiency electrophosphorescent devices. The molecular design is configured with carbazole as the hole-transporting block and N-phenylbenzimidazole as the electron-transporting block hybridized through the saturated bridge center (C9) and meta-conjugation site (C3) of fluorene, respectively. With structural topology tuning of the connecting manner between N-phenylbenzimidazole and the fluorene core, the resulting physical properties can be subtly modulated. Bipolar host CzFCBI with a C connectivity between phenylbenzimidazole and the fluorene bridge exhibited extended π conjugation; therefore, a low triplet energy of 2.52 eV was observed, which is insufficient to confine blue phosphorescence. However, the monochromatic devices indicate that the matched energy-level alignment allows CzFCBI to outperform its N-connected counterpart CzFNBI while employing other long-wavelength-emitting phosphorescent guests. In contrast, the high triplet energy (2.72 eV) of CzFNBI imparted by the N connectivity ensures its utilization as a universal bipolar host for blue-to-red phosphors. With a common device configuration, CzFNBI has been utilized to achieve highly efficient and low-roll-off devices with external quantum efficiency as high as 14 % blue, 17.8 % green, 16.6 % yellowish-green, 19.5 % yellow, and 18.6 % red. In addition, by combining yellowish-green with a sky-blue emitter and a red emitter, a CzFNBI-hosted single-emitting-layer all-phosphor three-color-based white electrophosphorescent device was successfully achieved with high efficiencies (18.4 %, 36.3 cd A(-1) , 28.3 lm W(-1) ) and highly stable chromaticity (CIE x=0.43-0.46 and CIE y=0.43) at an applied voltage of 8 to 12 V, and a high color-rendering index of 91.6.

Two new bipolar host molecules composed of hole-transporting carbazole and electron-transporting cyano (CzFCN) or oxadiazole (CzFOxa)-substituted fluorenes are synthesized and characterized. The non-conjugated connections, via an sp3-hybridized carbon, effectively block the electronic interactions between electron-donating and -accepting moieties, giving CzFCN and CzFOxa bipolar charge transport features with balanced mobilities (10−5 to 10−6 cm2 V−1 s−1). The meta–meta configuration of the fluorene-based acceptors allows the bipolar hosts to retain relatively high triplet energies [ET = 2.70 eV (CzFOxa) and 2. 86 eV (CzFCN)], which are sufficiently high for hosting blue phosphor. Using a common device structure – ITO/PEDOT:PSS/DTAF/TCTA/host:10% dopants (from blue to red)/DPPS/LiF/Al – highly efficient electrophosphorescent devices are successfully achieved. CzFCN-based devices demonstrate better performance characteristics, with maximum ηext of 15.1%, 17.9%, 17.4%, 18%, and 20% for blue (FIrpic), green [(PPy)2Ir(acac)], yellowish-green [m-(Tpm)2Ir(acac)], yellow [(Bt)2Ir(acac)], and red [Os(bpftz)2(PPhMe2)2, OS1], respectively. In addition, combining yellowish-green m-(Tpm)2Ir(acac) with a blue emitter (FIrpic) and a red emitter (OS1) within a single emitting layer hosted by bipolar CzFCN, three-color electrophosphorescent WOLEDs with high efficiencies (17.3%, 33.4 cd A−1, 30 lm W −1), high color stability, and high color-rendering index (CRI) of 89.7 can also be realized.

We demonstrate improving balance of carrier mobilities in neat-film light-emitting electrochemical cells (LECs) utilizing a cationic near-infrared laser dye as the carrier trapper. EL measurements show that the peak EQE reaches 12.75%, representing a 1.4 times enhancement in device efficiency as compared to that of the undoped neat-film LECs.

Preparation and characterization of a new class of emissive Os(II) complexes (1–5) have been achieved using 3-(thiazol-2-yl), 3-(benzothiazol-2-yl), 3-(imidazol-2-yl) and 3-(benzimidazol-2-yl) azole chelates, together with the incorporation of one diphosphine ancillary for satisfying the octahedral coordination arrangement. The resulting Os(II) complexes, except for 5, all show bright emission spanning visible region from green to saturated red, and their structural versus spectroscopic properties have been comprehended by absorption/emission together with computational approaches. Subsequently, a series of solution-processed OLEDs using 1–4 as the dopant were successfully fabricated, demonstrating excellent device performances with external quantum efficiency (EQE) of 15%, current efficiency exceeding 48 cd/A, and power conversion efficiency up to 50 lm/W. Complex 4 is the only Os(II) based phosphor so far suitable for the fabrication of highly efficient green-emitting OLEDs.

Non-precious metal catalysts of the oxygen reduction reaction are highly favored for use in polymer electrolyte fuel cells (PEFC) because of their relatively low cost. Here, a new carbon-black-supported pyrolyzed Co-corrole (py-Co-corrole/C) catalyst of the oxygen reduction reaction (ORR) in a PEFC cathode is demonstrated to have high catalytic performance. The py-Co-corrole/C at 700 °C exhibits optimized ORR activity and participates in a direct four-electron reduction pathway for the reduction of O2 to H2O. The H2-O2 PEFC test of py-Co-corrole/C in the cathode reveals a maximum power density of 275 mW cm−2, which yields a higher performance and a lower Co loading than previous studies of Co-based catalysts for PEFCs. The enhancement of the ORR activity of py-Co-corrole/C is attributable to the four-coordinated Co-corrole structure and the oxidation state of the central cobalt.

Derivatives of 5,7-dichloro-2-styrylquinoline (1), modified at position 8 of quinoline moiety with a methyl ether (4, DCSQM) or acetate (5, DCSQA), were synthesized and investigated. Both compounds exhibited high thermal stability (Td > 320 °C). The UV-vis absorption of DCSQM and DCSQA varied only slightly in different solvents, whereas the emission spectra showed pronounced red shifts with increasing solvent polarity, suggesting the intramolecular charge transfer character of the emission state. Compounds 4 and 5 can emit lights from blue to green color in different solvents. The solvent polarity dependent electronic transitions are attributed to efficient intramolecular charge transfer (ICT) processes, in which the HOMOs and LUMOs are localized on the styrene-based ring and the quinoline-based moiety, respectively. The quinoline-based LUMO provides compelling evidence that the first reduction site occurs on the electron-deficient quinoline moiety.

Highly efficient orange and green emission from single-layered solid-state light-emitting electrochemical cells based on cationic transition-metal complexes [Ir(ppy)2sb]PF6 and [Ir(dFppy)2sb]PF6 (where ppy is 2-phenylpyridine, dFppy is 2-(2,4-difluorophenyl)pyridine, and sb is 4,5-diaza-9,9′-spirobifluorene) is reported. Photoluminescence measurements show highly retained quantum yields for [Ir(ppy)2sb]PF6 and [Ir(dFppy)2 sb]PF6 in neat films (compared with quantum yields of these complexes dispersed in m-bis(N-carbazolyl)benzene films). The spiroconfigured sb ligands effectively enhance the steric hindrance of the complexes and reduce the self-quenching effect. The devices that use single-layered neat films of [Ir(ppy)2sb]PF6 and [Ir(dFppy)2sb]PF6 achieve high peak external quantum efficiencies and power efficiencies of 7.1 % and 22.6 lm W–1) at 2.5 V, and 7.1 % and 26.2 lm W–1 at 2.8 V, respectively. These efficiencies are among the highest reported for solid-state light-emitting electrochemical cells, and indicate that cationic transition-metal complexes containing ligands with good steric hindrance are excellent candidates for highly efficient solid-state electrochemical cells.

A convenient modified short-cut route for the preparation of a 32-membered octaazamacrocyclic molecule, 1,5,9,13,17,21,25,29-octaazacyclodotriacontane hydrochloride, [32]ane-N 8 .8HCl has been described. The proper tetramine has been contemplated to go this new pathway which propagates [32]-N 8 .8HCl more effectively.