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.

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.

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.

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 , IC-4F for , and IC-4Cl for ). Both halogenated NFAs, i.

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.

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.

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 -bisadduct by tether-directed functionalization of C via a multistep synthetic protocol.

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 as the donor, a narrow band gap non-fullerene acceptor , and a wide band gap PCBM. The OSCs based on optimized : (1:1.2) and :PCBM (1:1.

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 (PC 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:PC BM realized overall power conversion efficiency (PCE) of 10.66 % [short-circuit current density (J )=15.

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.

ScN@ -C 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-ScN@ -C donor-acceptor conjugate and its C analog, triphenylamine-thiophene-C conjugate is reported, and the significance of the thiophene spacer in promoting electron transfer events is unraveled.

Occurrence of excited state charge separation in a N-doped graphene-perylenediimide hybrid formed '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 chemistry, we have successfully synthesized a donor-acceptor hybrid comprised of N-doped graphene and perylenediimide (PDI), a well-known electron-accepting photosensitizer.

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.

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.

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.

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 PCBM is employed as the acceptor. Overall power conversion efficiencies of 8.

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

N-Doped graphene (N-G) was chemically functionalized by -alkylation with the well-known electron acceptor C. The degree of functionalization and the key structural features of the N-G/C 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 C while the fluorescence of C within the hybrid was found to be fully quenched.

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.

[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⋅CH 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.

Regioselectivity of the Pauson-Khand reaction in single-walled carbon nanotubes.

Chemical functionalization of nanotubes, in which their properties can be combined with those of other classes of materials, is fundamental to improve the physicochemical properties of nanotubes for potential technological applications. In this work, we theoretically and experimentally examine the Pauson-Khand reaction (PKR) on zig-zag, armchair, and chiral single-walled carbon nanotubes (SWCNTs). Our benchmarked density functional theory (DFT) calculations show that an alternative pathway to the widely accepted Magnus reaction pathway has significantly lower energy barriers, thus suggesting the use of this alternative pathway to predict whether a PKR on SWCNTs is favored or hampered.

Selective Screening of Biological Thiols by Means of an Unreported Magenta Interaction and Evaluation Using Smartphones.

The determination of biological thiols is considered to be of great interest because of the participation of these molecules in physiological disorders as indicators of their existence and progress, such as Alzheimer's disease, cancer, and cystic fibrosis, among others. Optical techniques for the quantification of these analytes are superior to other techniques in terms of selectivity, sensitivity, and cost. We describe here a simple protocol to determine biological thiols by means of a colorimetric analysis based on a magenta color interaction with 5,5'-dithiobis(2-nitrobenzoic acid).

Panchromatic ternary organic solar cells with 9.44% efficiency incorporating porphyrin-based donors.

In an effort to improve the short-circuit current and fill factor, organic solar cells have been developed with ternary blending in a single bulk heterojunction active layer. We report here several all small molecule organic solar cells based on ternary bulk heterojunction active layers. These layers consist of two small molecule porphyrin donors (MV71 and MV72), which have the same backbone but different end-capping acceptor units, and PC71BM as the acceptor.

Oligomers of cyclopentadithiophene-vinylene in aromatic and quinoidal versions and redox species with intermediate forms.

A new series of π-conjugated oligomers based on the 4,4 dihexyl-4-cyclopenta[2,1-:3,4-']dithiophene vinylene repeating unit has been prepared and characterized by X-ray, electrochemical, spectroscopic (UV-Vis absorption, emission and Raman) and density functional theory methods. The oligomers in their neutral, oxidized and reduced forms have been investigated. The neutral compounds show a longer mean conjugation length than oligothiophenes and oligothiophene-vinylenes and display very rich redox chemistry with the stabilization of polycationic states of which the radical cations and dications are strong NIR absorbers, the latter displaying singlet diradicaloid character.

Edge-on and face-on functionalized Pc on enriched semiconducting SWCNT hybrids.

Enriched semiconducting single-walled carbon nanotubes (SWCNT (6,5) and SWCNT (7,6)) and HiPco nanotubes were covalently functionalized with either zinc phthalocyanine or silicon phthalocyanine as electron donors. The synthetic strategy resulted in edge-on and face-on geometries with respect to the phthalocyanine geometry, with both phthalocyanines held by an electronically conducting diphenylacetylene linker. The extent of functionalization in the MPc-SWCNT (M = Zn or Si) donor-acceptor nanohybrids was determined by systematic studies involving AFM, TGA, XPS, optical and Raman techniques.