Dibenzoquinone Cyclopentadithiophene Diradicaloids Show Optical Transitions of Different Spin States and Anomalous Near-Infrared Emission.

We have prepared a series of bis(semiquinone) compounds with dithiophene bridges of different length that evolve from closed-shell (smaller compound) to full diradical (longer compound) for which the narrow singlet-triplet energy gap allows the triplet population at 298 K. The medium size system has a variety of photonic properties with absorptions and emission in the optical near-infrared region mediated by a unique case of anti-Kasha emission. A whole set of optical absorption/emission and vibrational steady state spectroscopies as well as picosecond transient absorption spectroscopy, all complemented with spectroelectrochemistry and theoretical calculations, is presented.

Organic Solar Cells Based on Non-Fullerene Low Molecular Weight Organic Semiconductor Molecules.

The development of narrow bandgap A-D-A- and ADA'DA-type non-fullerene small molecule acceptors (NFSMAs) along with small molecule donors (SMDs) have led to significant progress in all-small molecule organic solar cells. Remarkable power conversion efficiencies, nearing the range of 17-18 %, have been realized. These efficiency values are on par with those achieved in OSCs based on polymeric donors. The commercial application of organic photovoltaic technology requires the design of more efficient organic conjugated small molecule donors and acceptors. In recent years the precise tuning of optoelectronic properties in small molecule donors and acceptors has attracted considerable attention and has contributed greatly to the advancement of all-SM-OSCs. Several reviews have been published in this field, but the focus of this review concerns the advances in research on OSCs using SMDs and NFSMAs from 2018 to the present. The review covers the progress made in binary and ternary OSCs, the effects of solid additives on the performance of all-SM-OSCs, and the recently developed layer-by-layer deposition method for these OSCs. Finally, we present our perspectives and a concise outlook on further advances in all-SM-OSCs for their commercial application.

p-Type Functionalized Carbon Nanohorns and Nanotubes in Perovskite Solar Cells.

The incorporation of p-type functionalized carbon nanohorns (CNHs) in perovskite solar cells (PSCs) and their comparison with p-type functionalized single- and double-walled carbon nanotubes (SWCNTs and DWCNTs) are reported in this study for the first time. These p-type functionalized carbon nanomaterial (CNM) derivatives were successfully synthesized by [2 + 1] cycloaddition reaction with nitrenes formed from triphenylamine (TPA) and 9-phenyl carbazole (Cz)-based azides, yielding CNHs-TPA, CNHs-Cz, SWCNTs-Cz, SWCNTs-TPA, DWCNTs-TPA, and DWCNTs-Cz. These six novel CNMs were incorporated into the spiro-OMeTAD-based hole transport layer (HTL) to evaluate their impact on regular mesoporous PSCs. The photovoltaic results indicate that all p-type functionalized CNMs significantly improve the power conversion efficiency (PCE), mainly by enhancing the short-circuit current density (Jsc) and fill factor (FF). TPA-functionalized derivatives increased the PCE by 12-17% compared to the control device without CNMs, while Cz-functionalized derivatives resulted in a PCE increase of 4-8%. Devices prepared with p-type functionalized CNHs exhibited a slightly better PCE compared with those based on SWCNTs and DWCNTs derivatives. The increase in hole mobility of spiro-OMeTAD, additional p-type doping, better energy alignment with the perovskite layer, and enhanced morphology and contact interface play important roles in enhancing the performance of the device. Furthermore, the incorporation of p-type functionalized CNMs into the spiro-OMeTAD layer increased device stability by improving the hydrophobicity of the layer and enhancing the hole transport across the MAPI/spiro-OMeTAD interface. After 28 days under ambient conditions and darkness, TPA-functionalized CNMs maintained the performance of the device by over 90%, while Cz-functionalized CNMs preserved it between 75 and 85%.

Effects of Halogenation on Cyclopentadithiophenevinylene-Based Acceptors with Excellent Responses in Binary Organic Solar Cells.

In recent years, non-fused non-fullerene acceptors (NFAs) have attracted increasing consideration due to several advantages, which include simple preparation, superior yield, and low cost. In the work reported here, we designed and synthesized three new NFAs with the same cyclopentadithiophenevinylene (CPDTV) trimer as the electron-donating unit and different terminal units (IC for FG10, IC-4F for FG8, and IC-4Cl for FG6). Both halogenated NFAs, i.e., FG6 and FG8, show red-shifted absorption spectra and higher electron mobilities (more pronounced for FG6) in comparison with FG10. Moreover, the dielectric constants of these materials also increased upon halogenation of the IC terminal units, thus leading to a reduction in the exciton binding energy, which is favorable for dissociation of excitons and subsequent charge transfer despite the driving force (highest occupied molecular orbital and lowest unoccupied molecular orbital offsets) being very small. The organic solar cells (OSCs) constructed using these acceptors and PBDB-T, as the donor, showed PCE values of 15.08, 12.56, and 9.04% for FG6, FG8, and FG10, respectively. The energy loss for the FG6-based device was the lowest (0.45 eV) of all the devices, and this may be attributed to it having the highest dielectric constant, which leads to a reduction in the binding energy of exciton and a small driving force for hole transfer from FG6 to PBDB-T. The results indicate that the NFA containing the CPDTV oligomer core and halogenated terminal units can efficiently spread the absorption spectrum to the NIR zone. Non-fused NFAs have a bright future in the quest to obtain efficient OSCs with low cost for marketable purposes.

Formation and Photoinduced Electron Transfer in Porphyrin- and Phthalocyanine-Bearing N-Doped Graphene Hybrids Synthesized by Click Chemistry.

Graphene doped with heteroatoms such as nitrogen, boron, and phosphorous by replacing some of the skeletal carbon atoms is emerging as an important class of two-dimensional materials as it offers the much-needed bandgap for optoelectronic applications and provides better access for chemical functionalization at the heteroatom sites. Covalent grafting of photosensitizers onto such doped graphenes makes them extremely useful for light-induced applications. Herein, we report the covalent functionalization of N-doped graphene (NG) with two well-known electron donor photosensitizers, namely, zinc porphyrin (ZnP) and zinc phthalocyanine (ZnPc), using the simple click chemistry approach. Covalent attachment of ZnP and ZnPc at the N-sites of NG in NG-ZnP and NG-ZnPc hybrids was confirmed by using a range of spectroscopic, thermogravimetric and imaging techniques. Ground- and excited-state interactions in NG-ZnP and NG-ZnPc were monitored by using spectral and electrochemical techniques. Efficient quenching of photosensitizer fluorescence in these hybrids was observed, and the relatively easier oxidations of ZnP and ZnPc supported excited-state charge-separation events. Photoinduced charge separation in NG-ZnP and NG-ZnPc hybrids was confirmed by using the ultrafast pump-probe technique. The measured rate constants were of the order of 1010  s,-1 thus indicating ultrafast electron transfer phenomena.

Gold(III) Porphyrin Was Used as an Electron Acceptor for Efficient Organic Solar Cells.

The widespread use of nonfullerene-based electron-accepting materials has triggered a rapid increase in the performance of organic photovoltaic devices. However, the number of efficient acceptor compounds available is rather limited, which hinders the discovery of new, high-performing donor:acceptor combinations. Here, we present a new, efficient electron-accepting compound based on a hitherto unexplored family of well-known molecules: gold porphyrins. The electronic properties of our electron-accepting gold porphyrin, named VC10, were studied by UV-Vis spectroscopy and by cyclic voltammetry (CV) , revealing two intense optical absorption bands at 500-600 and 700-920 nm and an optical bandgap of 1.39 eV. Blending VC10 with PTB7-Th, a donor polymer, which gives rise to an absorption band at 550-780 nm complementary to that of VC10, enables the fabrication of organic solar cells (OSCs) featuring a power conversion efficiency of 9.24% and an energy loss of 0.52 eV. Hence, this work establishes a new approach in the search for efficient acceptor molecules for solar cells and new guidelines for future photovoltaic material design.

Self-Assembly-Directed Organization of a Fullerene-Bisporphyrin into Supramolecular Giant Donut Structures for Excited-State Charge Stabilization.

Functional materials composed of spontaneously self-assembled electron donor and acceptor entities capable of generating long-lived charge-separated states upon photoillumination are in great demand as they are key in building the next generation of light energy harvesting devices. However, creating such well-defined architectures is challenging due to the intricate molecular design, multistep synthesis, and issues associated in demonstrating long-lived electron transfer. In this study, we have accomplished these tasks and report the synthesis of a new fullerene-bis-Zn-porphyrin e-bisadduct by tether-directed functionalization of C60 via a multistep synthetic protocol. Supramolecular oligomers were subsequently formed involving the two porphyrin-bearing arms embracing a fullerene cage of the vicinal molecule as confirmed by MALDI-TOF spectrometry and variable temperature NMR. In addition, the initially formed worm-like oligomers are shown to evolve to generate donut-like aggregates by AFM monitoring that was also supported by theoretical calculations. The final supramolecular donuts revealed an inner cavity size estimated as 23 nm, close to that observed in photosynthetic antenna systems. Upon systematic spectral, computational, and electrochemical studies, an energy level diagram was established to visualize the thermodynamic feasibility of electron transfer in these donor-acceptor constructs. Subsequently, transient pump-probe spectral studies covering the wide femtosecond-to-millisecond time scale were performed to confirm the formation of long-lived charge-separated states. The lifetime of the final charge-separated state was about 40 µs, thus highlighting the significance of the current approach of building giant self-organized donor-acceptor assemblies for light energy harvesting applications.

Fullerene/Non-fullerene Alloy for High-Performance All-Small-Molecule Organic Solar Cells.

Organic solar cells (OSCs) that contain small molecules only were prepared with FG1 as the donor, a narrow band gap non-fullerene acceptor MPU4, and a wide band gap PC71BM. The OSCs based on optimized FG1:MPU4 (1:1.2) and FG1:PC71BM (1:1.5) active layers, respectively, gave power conversion efficiencies (PCEs) of 11.18% with a short circuit current (JSC) of 19.54 mA/cm2, open circuit voltage (VOC) of 0.97 V, and fill factor (FF) of 0.59, and 6.62% with a JSC of 12.50 mA/cm2, VOC of 0.84 V, and FF of 0.63%, respectively. A PCE of 13.26% was obtained from the optimized ternary FG1:PC71BM:MPU4 (1:0.3:0.9) OSCs and this arises because of the boost in a JSC of 21.91 mA/cm2 and FF of 0.68. The VOC of the ternary OSCs (0.89 V) lies between those for the OSCs based on FG1:MPU4 and FG1:PC71BM, which indicates the formation of an alloy of the two acceptors. The increase in JSC and FF in the ternary OSCs may result from the efficient energy transfer from PC71BM to MPU4 as well as more charge-transfer donor/acceptor interfaces, enhanced charge carrier mobilities resulting in better adjusted charge transport, and lower bimolecular and trap-assisted recombination. The appropriate phase separation, increased crystallinity, and reduced π-π stacking distance in the ternary active layer are consistent with the enhancement in the FF for OSCs based on a ternary active layer. The results of this work suggest the merging of the fullerene acceptor into the non-fullerene acceptor to form a fullerene/non-fullerene acceptor alloy, and this may be a viable approach to obtain high-performance OSCs.

Reducing Energy Loss in Organic Solar Cells by Changing the Central Metal in Metalloporphyrins.

The effect of central donor core on the properties of A-π-D-π-A donors, where D is a porphyrin macrocycle, cyclopenta[2,1-b:3,4-b']dithiophene is the π bridge, and A is a dicyanorhodanine terminal unit, was investigated for the fabrication of the organic solar cells (OSCs), along [6,6]-phenyl-C71-butyric acid methyl ester (PC71 BM) as electron acceptor. A new molecule consisting of Ni-porphyrin central donor core (VC9) showed deep HOMO energy level and OSCs based on optimized VC9:PC71 BM realized overall power conversion efficiency (PCE) of 10.66 % [short-circuit current density (JSC )=15.48 mA/cm2 , fill factor (FF)=0.65] with high open circuit voltage (VOC ) of 1.06 V and very low energy loss of 0.49 eV, whereas the Zn-porphyrin analogue VC8:PC71 BM showed PCE of 9.69 % with VOC of 0.89 V, JSC of 16.25 mA/cm2 and FF of 0.67. Although the OSCs based on VC8 showed higher JSC in comparison to VC9, originating from the broader absorption profile of VC8 that led to more exciton generation, the higher value of PCE of VC9 is owing to the higher VOC and reduced energy loss.

Triplet photosensitizer-nanotube conjugates: synthesis, characterization and photochemistry of charge stabilizing, palladium porphyrin/carbon nanotube conjugates.

The ability of a triplet photosensitizer to generate long-lived charge separated states, in contrast to traditionally used singlet photosensitizers, in covalently functionalized single-walled carbon nanotube hybrids has been investigated. Enriched single-walled carbon nanotubes with two diameters, namely (6,5) and (7,6), were covalently modified to carry a charge-stabilizing triplet photosensitizer derived from a palladium porphyrin. The nanohybrids were fully characterized and the presence of intramolecular interactions between the porphyrin and nanotubes was established from various spectroscopic, imaging, electrochemical and thermochemical studies. Photoluminescence of palladium porphyrin was found to be quantitatively quenched in the presence of covalently appended SWCNTs and this quenching is due to excited state charge separation and has been established by femtosecond transient absorption studies. Owing to the presence of the triplet photosensitizer, the charge separated states lasted over 3 ns, i.e., much longer than those reported earlier for singlet photosensitizer-derived nanotube hybrids. The nanohybrids also exhibited efficient photocatalytic behavior in experiments involving electron pooling of one-electron reduced methyl viologen in the presence of a sacrificial electron donor. Higher yields of photoproducts were achieved from the present donor-acceptor nanohybrids when compared with those of singlet photosensitizer-derived nanohybrids, more so for (6,5) nanotube derived hybrids compared to (7,6) nanotube derived hybrids. The present findings highlight the importance of triplet photosensitizer derived nanohybrids in artificial photosynthesis of charge separation and photocatalytic applicatons.

Synthesis and electronic properties of pyridine end-capped cyclopentadithiophene-vinylene oligomers.

A series of four oligomers of cyclopentadithiophene-vinylenes end capped with pyridine groups was prepared and their optical and electronic properties studied. Treatment with trifluoroacetic acid (TFA) leads to the bisprotonation of the nitrogens of the pyridine, which has an important impact on the optical properties. Excess treatment with TFA provokes the oxidation of the conjugated core, generating radical cations and dications. The ease of the TFA treatment in solution was extended to protonation in the solid-state where further characterization of the neutral and TFA-treated samples was carried out in electrically active substrates in organic field-effect transistors. Finally, the new molecules were found to be excellent conductors in single-molecule junctions thanks to strong electron delocalization and resonance orbital mediated transport. These studies show the opening of a spectrum of possibilities by suitable terminal substitution of π-cores.

Sc3N@I h -C80 based donor-acceptor conjugate: role of thiophene spacer in promoting ultrafast excited state charge separation.

Light induced charge separation in a newly synthesized triphenylamine-thiophene-Sc3N@I h -C80 donor-acceptor conjugate and its C60 analog, triphenylamine-thiophene-C60 conjugate is reported, and the significance of the thiophene spacer in promoting electron transfer events is unraveled.

Bidirectional charge-transfer behavior in carbon-based hybrid nanomaterials.

In recent years there has been a growing interest in finding materials revealing bidirectional charge-transfer characteristics, that is, materials behaving as an electron donor or an acceptor in the presence of redox and photoactive addends, for optoelectronic applications. In this respect, carbon-based nanostructures, such as graphene and carbon nanotubes, have emerged as promising nanomaterials for the development of hybrid systems for bidirectional charge transfer, whose behaviour can be switched from donor-type to acceptor-type by simply changing the electroactive counterpart to which they are anchored. In this review we provide an overview of the main advances that have been made over the past few years in carbon-based hybrid architectures involving different types of carbon nanostructures and photosensitizers. In particular, carbon nanotube and graphene-based hybrid systems will be highlighted.

Modulating charge carrier density and mobility in doped graphene by covalent functionalization.

Covalent B-functionalization of B-doped graphene has been performed for the first time. The electronic properties and Hall effect of functionalized N- and B-doped graphene can be tuned by tailoring the electron-donating/-withdrawing properties of the organic addend.

Cycloaddition of Nitrile Oxides to Graphene: a Theoretical and Experimental Approach.

Density functional theory (DFT) studies of the interaction between graphene sheets and nitrile oxides have proved the feasibility of the reaction through 1,3-dipolar cycloaddition. The viability of the approach has been also confirmed experimentally through the cycloaddition of few-layer exfoliated graphene and nitrile oxides containing functional organic groups with different electronic nature. The cycloaddition reaction has been successfully achieved in one-pot from the corresponding oximes under microwave (MW) irradiation. The successful formation of the isoxazoline ring has been confirmed by Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR), thermogravimetric analysis (TGA) and X-ray photoelectron spectroscopy (XPS).

Near-IR Absorbing D-A-D Zn-Porphyrin-Based Small-Molecule Donors for Organic Solar Cells with Low-Voltage Loss.

Two D-A-D small molecules with a DPP acceptor core and Zn-porphyrin donor with different electron-donating substituents, namely, 2,6-bis(dodecyloxy)phenyl and 5-hexylthieno[3,2- b]thiophen-2-yl at mesopositions, VC4 and VC5, were synthesized, and their optical and electrochemical properties were investigated. The results reveal that both molecules are suitable as donors for organic solar cells (OSCs) in which PC71BM is employed as the acceptor. Overall power conversion efficiencies of 8.05% ( Jsc = 13.83 mA/cm2, Voc = 0.91 V, and FF = 0.64) and 8.89% ( Jsc = 16.98 mA/cm2, Voc = 0.79 V, and FF = 0.663) were obtained, respectively. The high Voc value for the VC4-based OSC correlates with the deeper HOMO, whereas the high Jsc value for VC5 may be attributed to the extended absorption spectrum toward the longer wavelength region. Moreover, the relatively high FF value for VC5-based OSCs as compared to the VC4 counterparts may be related to the more balanced charge transport in the active layer, reduced charge recombination, and efficient charge collection. The energy loss for VC5 is smaller (0.52 eV) than that for VC4 (0.56 eV).

Occurrence of excited state charge separation in a N-doped graphene-perylenediimide hybrid formed via 'click' chemistry.

Hetero-atom doped graphene is a two-dimensional material with a band gap, needed to build optoelectronic devices. However, research progress in this area has been sluggish due to synthetic challenges to build energy harvesting materials, especially donor-acceptor type hybrids. In the present study, using click chemistry, we have successfully synthesized a donor-acceptor hybrid comprised of N-doped graphene and perylenediimide (PDI), a well-known electron-accepting photosensitizer. The TGA and XPS results revealed the attachment of the PDI moiety in the hybrid. Ground and excited state interactions were monitored by a variety of spectral and electrochemical techniques. Finally, the ability of the present donor-acceptor hybrid to undergo photoinduced charge separation from singlet excited PDI was systematically probed using femtosecond transient spectral techniques. Evidence of charge separation was possible to achieve from comparison of transient and spectroelectrochemical results. These results suggest the potential use of covalently functionalized, substitutional N-doped graphene as a functional material for building optoelectronic devices.

[All]-S,S-dioxide Oligo-Thienylenevinylenes: Synthesis and Structural/Electronic Shapes from Their Molecular Force Fields.

Oligo-S,S-dioxothienylenevinylenes have been prepared by transferring oxygen atoms to the sulfur atoms using the HOF⋅CH3 CN complex. Their photophysical properties are presented in comparison with their thiophenevinylene congeners. Together with their vibrational properties and molecular force fields, this study allows for the interpretation of the alteration of aromaticity and inter-ring exocyclic π-conjugation in this series.

Ni-Porphyrin-based small molecule for efficient organic solar cells (>9.0%) with a high open circuit voltage of over 1.0 V and low energy loss.

A new A-π-D-π-A small molecule with a Ni-porphyrin core (MV143) has been synthesized and employed as a donor, along with PC71BM, for the fabrication of solution-processed bulk heterojunction OSCs organic solar cells. The device exhibited an overall PCE of 9.14% (JSC = 13.87 mA cm-2, VOC = 1.08 V and FF = 0.61) and a low photon energy loss of 0.52 eV.

N-Doped graphene/C60 covalent hybrid as a new material for energy harvesting applications.

N-Doped graphene (N-G) was chemically functionalized by N-alkylation with the well-known electron acceptor C60. The degree of functionalization and the key structural features of the N-G/C60 hybrid were systematically investigated by a number of techniques including thermogravimetric analysis, X-ray photoelectron and Raman spectroscopies and transmission electron and atomic force microscopies. Absorption and electrochemical studies revealed interactions between the N-G and C60 while the fluorescence of C60 within the hybrid was found to be fully quenched. Evidence for the occurrence of excited state charge transfer from the singlet excited C60 to N-G in the hybrid was obtained from femtosecond transient absorption studies covering the visible-near-IR regions. Electron-pooling experiments performed in the presence of a sacrificial electron donor and a second electron acceptor, methyl viologen, revealed the accumulation of the one-electron reduced product of methyl viologen upon continuous irradiation of the N-G/C60 nanohybrid, thus revealing the utility of this material in photocatalytic energy harvesting applications.