Highly Efficient Doping of Conjugated Polymers Using Multielectron Acceptor Salts.

Chemical doping is a vital tool for tuning electronic properties of conjugated polymers. Most single electron acceptors used for p-doping necessitate high dopant concentrations to achieve good electrical conductivity. However, high-molar doping ratios hamper doping efficiency. Here a new concept of using multielectron acceptor (MEA) salts as dopants for conjugated polymers is presented. Two novel MEA salts are synthesized and their doping efficiency towards two polymers differing in their dielectric properties are compared with two single electron acceptors such as NOPF6 and magic blue. Cutting-edge methods such as ultraviolet photoelectron spectroscopy/X-ray photoelectron spectroscopy (XPS), impedance spectroscopy, and density of states analysis in addition to UV-vis-NIR absorption, spectroelectrochemistry, and Raman spectroscopy methods are used to characterize the doped systems. The tetracation salt improves the conductivity by two orders of magnitude and quadruples the charge carrier concentration compared to single electron acceptors for the same molar ratio. The differences in charge carrier density and activation energy on doping are delineated. Further, a strong dependency of the carrier release on the polymer polarity is observed. High carrier densities at reduced dopant loadings and improved doping efficacies using MEA dopants offer a highly efficient doping strategy for conjugated polymers.

Heteroleptic Copper(I) Complexes Prepared from Phenanthroline and Bis-Phosphine Ligands: Rationalization of the Photophysical and Electrochemical Properties.

The electronic and structural properties of ten heteroleptic [Cu(NN)(PP)]+ complexes have been investigated. NN indicates 1,10-phenanthroline (phen) or 4,7-diphenyl-1,10-phenanthroline (Bphen); each of these ligands is combined with five PP bis-phosphine chelators, i.e., bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,2-bis(diphenylphosphino)benzene (dppb), and bis[(2-diphenylphosphino)phenyl] ether (POP). All complexes are mononuclear, apart from those based on dppm, which are dinuclear. Experimental data-also taken from the literature and including electrochemical properties, X-ray crystal structures, UV-vis absorption spectra in CH2Cl2, luminescence spectra and lifetimes in solution, in PMMA, and as powders-have been rationalized with the support of density functional theory calculations. Temperature dependent studies (78-358 K) have been performed for selected complexes to assess thermally activated delayed fluorescence. The main findings are (i) dependence of the ground-state geometry on the crystallization conditions, with the same complex often yielding different crystal structures; (ii) simple model compounds with imposed C2 v symmetry ([Cu(phen)(PX3)2]+; X = H or CH3) are capable of modeling structural parameters as a function of the P-Cu-P bite angle, which plays a key role in dictating the overall structure of [Cu(NN)(PP)]+ complexes; (iii) as the P-Cu-P angle increases, the energy of the metal-to-ligand charge transfer absorption bands linearly increases; (iv) the former correlation does not hold for emission spectra, which are red-shifted for the weaker luminophores; (v) the larger the number of intramolecular π-interactions within the complex in the ground state, the higher the luminescence quantum yield, underpinning a geometry locking effect that limits the structural flattening of the excited state. This work provides a general framework to rationalize the structure-property relationships of [Cu(NN)(PP)]+, a class of compounds of increasing relevance for electroluminescent devices, photoredox catalysis, and solar-to-fuels conversion, which so far have been investigated in an unsystematic fashion, eluding a comprehensive understanding.

Efficient Photoinduced Energy and Electron Transfer in ZnII -Porphyrin/Fullerene Dyads with Interchromophoric Distances up to 2.6†nm and No Wire-like Connectivity.

The dyads 1-3 made of an alkynylated ZnII -porphyrin and a bis-methanofullerene derivative connected through a copper-catalyzed azide-alkyne cycloaddition have been synthesized. The porphyrin and fullerene chromophores are separated through a bridge made of a bismethanofullerene tether linked to different spacers conjugated to the porphyrin moiety [i.e., m-phenylene (1), p-phenylene (2), di-p-phenylene-ethynylene (3)]. Compounds 1-3 exhibit relatively rigid structures with an interchromophoric separation of 1.7, 2.0, and 2.6 nm, respectively, and no face-to-face or direct through-bond conjugation. The photophysical properties of compounds 1-3 have been investigated in toluene and benzonitrile with steady-state and time-resolved techniques as well as model calculations on the Förster energy transfer. Excited-state interchromophoric electronic interactions are observed with a distinct solvent and distance dependence. The latter effect is evidenced in benzonitrile, where compounds 1 and 2 exhibit a photoinduced electron transfer in the Marcus-inverted region, with charge-separated (CS) states living for 0.44 and 0.59 µs, respectively, whereas compound 3 only undergoes energy transfer, as in apolar toluene. The quantum yield of the charge separation (φCS ) of compounds 1 and 2 in benzonitrile is ≥0.75. It is therefore demonstrated that photoinduced energy and electron transfers in porphyrin-fullerene systems with long interchromophoric distances may efficiently occur also when the bridge does not provide a wire-like conjugation and proceed through the triplet states of the chromophoric moieties.

Solvent Molding of Organic Morphologies Made of Supramolecular Chiral Polymers.

The self-assembly and self-organization behavior of uracil-conjugated enantiopure (R)- or (S)-1,1'-binaphthyl-2,2'-diol (BINOL) and a hydrophobic oligo(p-phenylene ethynylene) (OPE) chromophore exposing 2,6-di(acetylamino)pyridine termini are reported. Systematic spectroscopic (UV-vis, CD, fluorescence, NMR, and SAXS) and microscopic studies (TEM and AFM) showed that BINOL and OPE compounds undergo triple H-bonding recognition, generating different organic nanostructures in solution. Depending on the solvophobic properties of the liquid media (toluene, CHCl3, CHCl3/CHX, and CHX/THF), spherical, rod-like, fibrous, and helical morphologies were obtained, with the latter being the only nanostructures expressing chirality at the microscopic level. SAXS analysis combined with molecular modeling simulations showed that the helical superstructures are composed of dimeric double-cable tape-like structures that, in turn, are supercoiled at the microscale. This behavior is interpreted as a consequence of an interplay among the degree of association of the H-bonded recognition, the vapor pressure of the solvent, and the solvophobic/solvophilic character of the supramolecular adducts in the different solutions under static and dynamic conditions, namely solvent evaporation conditions at room temperature.

NiOx Passivation in Perovskite Solar Cells: From Surface Reactivity to Device Performance.

Nonstoichiometric nickel oxide (NiOx) is one of the very few metal oxides successfully used as hole extraction layer in p-i-n type perovskite solar cells (PSCs). Its favorable optoelectronic properties and facile large-scale preparation methods are potentially relevant for future commercialization of PSCs, though currently low operational stability of PSCs is reported when a NiOx hole extraction layer is used in direct contact with the perovskite absorber. Poorly understood degradation reactions at this interface are seen as cause for the inferior stability, and a variety of interface passivation approaches have been shown to be effective in improving the overall solar cell performance. To gain a better understanding of the processes happening at this interface, we systematically passivated specific defects on NiOx with three different categories of organic/inorganic compounds. The effects on NiOx and the perovskite (MAPbI3) deposited on top were investigated using X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), and scanning electron microscopy (SEM). Here, we find that the perovskite's structural stability and film formation can be significantly affected by the passivation treatment of the NiOx surface. In combination with density functional theory (DFT) calculations, a likely origin of NiOx-perovskite degradation interactions is proposed. The surface passivated NiOx layers were incorporated into MAPbI3-based PSCs, and the influence on device performance and operational stability was investigated by current-voltage (J-V) characterization, impedance spectroscopy (IS), and open circuit voltage decay (OCVD) measurements. Interestingly, we find that a superior structural stability due to interface passivation must not relate to high operational stability. The discrepancy comes from the formation of excess ions at the interface, which negatively impacts all solar cell parameters.

Tuning photoinduced processes of covalently bound isoalloxazine and anthraquinone bichromophores.

We present here the synthesis of several new isoalloxazine cyclophanes containing electroactive anthraquinones linked by aliphatic chains of different lengths. Such structural changes provide different interchromophoric orientations leading to the tuning of the rate of the photoinduced electron transfer process from the anthraquinone unit towards the isoalloxazine singlet excited state. Molecular modelling studies were undertaken in order to determine the minimal energy of the proposed structures using Monte Carlo calculations (Amber, Macromodel v.8.1). The compounds have been fully characterised by NMR spectroscopy and the solid state structures of some of the macrocycles have been elucidated. The photophysical studies have been carried out in order to investigate the influence of π-π stacking on the optical properties of the macrocycles.

Heteroleptic copper(I) complexes prepared from phenanthroline and bis-phosphine ligands.

Preparation of [Cu(NN)(PP)](+) derivatives has been systematically investigated starting from two libraries of phenanthroline (NN) derivatives and bis-phosphine (PP) ligands, namely, (A) 1,10-phenanthroline (phen), neocuproine (2,9-dimethyl-1,10-phenanthroline, dmp), bathophenanthroline (4,7-diphenyl-1,10-phenanthroline, Bphen), 2,9-diphenethyl-1,10-phenanthroline (dpep), and 2,9-diphenyl-1,10-phenanthroline (dpp); (B) bis(diphenylphosphino)methane (dppm), 1,2-bis(diphenylphosphino)ethane (dppe), 1,3-bis(diphenylphosphino)propane (dppp), 1,2-bis(diphenylphosphino)benzene (dppb), 1,1'-bis(diphenylphosphino)ferrocene (dppFc), and bis[(2-diphenylphosphino)phenyl] ether (POP). Whatever the bis-phosphine ligand, stable heteroleptic [Cu(NN)(PP)](+) complexes are obtained from the 2,9-unsubstituted-1,10-phenanthroline ligands (phen and Bphen). By contrast, heteroleptic complexes obtained from dmp and dpep are stable in the solid state, but a dynamic ligand exchange reaction is systematically observed in solution, and the homoleptic/heteroleptic ratio is highly dependent on the bis-phosphine ligand. Detailed analysis revealed that the dynamic equilibrium resulting from ligand exchange reactions is mainly influenced by the relative thermodynamic stability of the different possible complexes. Finally, in the case of dpp, only homoleptic complexes were obtained whatever the bis-phosphine ligand. Obviously, steric effects resulting from the presence of the bulky phenyl rings on the dpp ligand destabilize the heteroleptic [Cu(NN)(PP)](+) complexes. In addition to the remarkable thermodynamic stability of [Cu(dpp)2]BF4, this negative steric effect drives the dynamic complexation scenario toward almost exclusive formation of homoleptic [Cu(NN)2](+) and [Cu(PP)2](+) complexes. This work provides the definitive rationalization of the stability of [Cu(NN)(PP)](+) complexes, marking the way for future developments in this field.

Modular engineering of H-bonded supramolecular polymers for reversible functionalization of carbon nanotubes.

A H-bond-driven, noncovalent, reversible solubilization/functionalization of multiwalled carbon nanotubes (MWCNTs) in apolar organic solvents (CHCl(3), CH(2)Cl(2), and toluene) has been accomplished through a dynamic combination of self-assembly and self-organization processes leading to the formation of supramolecular polymers, which enfold around the outer wall of the MWCNTs. To this end, a library of phenylacetylene molecular scaffolds with complementary recognition sites at their extremities has been synthesized. They exhibit triple parallel H-bonds between the NH-N-NH (DAD) functions of 2,6-di(acetylamino)pyridine and the CO-NH-CO (ADA) imidic groups of uracil derivatives. These residues are placed at 180° relative to each other (linear systems) or at 60°/120° (angular modules), in order to tune their ability of wrapping around MWCNTs. Molecular Dynamics (MD) simulations showed that the formation of the hybrid assembly MWCNT•[X•Y](n) (where X = 1a or 1b -DAD- and Y = 2, 3, or 4 -ADA-) is attributed to π-π and CH-π interactions between the graphitic walls of the carbon materials and the oligophenyleneethynylene polymer backbones along with its alkyl groups, respectively. Addition of polar or protic solvents, such as DMSO or MeOH, causes the disruption of the H-bonds with partial detachment of the polymer from the CNTs, followed by precipitation. Taking advantage of the chromophoric and luminescence properties of the molecular subunits, the solubilization/precipitation processes have been monitored by UV-vis absorption and luminescence spectroscopies. All hybrid MWCNTs-polymer materials have been also structurally characterized via thermogravimetric analysis (TGA), transmission electron microscopy (TEM), atomic force microscopy (AFM), scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS).

Nanostructured Hybrid Metal Mesh as Transparent Conducting Electrodes: Selection Criteria Verification in Perovskite Solar Cells.

Nanostructured metal mesh structures demonstrating excellent conductivity and high transparency are one of the promising transparent conducting electrode (TCE) alternatives for indium tin oxide (ITO). Often, these metal nanostructures are to be employed as hybrids along with a conducting filler layer to collect charge carriers from the network voids and to minimize current and voltage losses. The influence of filler layers on dictating the extent of such ohmic loss is complex. Here, we used a general numerical model to correlate the sheet resistance of the filler, lateral charge transport distance in network voids, metal mesh line width and ohmic losses in optoelectronic devices. To verify this correlation, we prepared gold or copper network electrodes with different line widths and different filler layers, and applied them as TCEs in perovskite solar cells. We show that the photovoltaic parameters scale with the hybrid metal network TCE properties and an Au-network or Cu-network with aluminum-doped zinc oxide (AZO) filler can replace ITO very well, validating our theoretical predictions. Thus, the proposed model could be employed to select an appropriate filler layer for a specific metal mesh electrode geometry and dimensions to overcome the possible ohmic losses in optoelectronic devices.

HOMO-HOMO Electron Transfer: An Elegant Strategy for p-Type Doping of Polymer Semiconductors toward Thermoelectric Applications.

Unlike the conventional p-doping of organic semiconductors (OSCs) using acceptors, here, an efficient doping concept for diketopyrrolopyrrole-based polymer PDPP[T]2 -EDOT (OSC-1) is presented using an oxidized p-type semiconductor, Spiro-OMeTAD(TFSI)2 (OSC-2), exploiting electron transfer from HOMOOSC-1 to HOMOOSC-2 . A shift of work function toward the HOMOOSC-1 upon doping is confirmed by ultraviolet photoelectron spectroscopy (UPS). Detailed X-ray photoelectron spectroscopy (XPS) and UV-vis-NIR absorption studies confirm HOMOOSC-1 to HOMOOSC-2 electron transfer. The reduction products of Spiro-OMeTAD(TFSI)2 to Spiro-OMeTAD(TFSI) and Spiro-OMeTAD is also confirmed and their relative amounts in doped samples is determined. Mott-Schottky analysis shows two orders of magnitude increase in free charge carrier density and one order of magnitude increase in the charge carrier mobility. The conductivity increases considerably by four orders of magnitude to a maximum of 10 S m-1 for a very low doping ratio of 8 mol%. The doped polymer films exhibit high thermal and ambient stability resulting in a maximum power factor of 0.07 µW m-1  K-2 at a Seebeck coefficient of 140 µV K-1 for a very low doping ratio of 4 mol%. Also, the concept of HOMOOSC-1 to HOMOOSC-2 electron transfer is a highly efficient, stable and generic way to p-dope other conjugated polymers.

Controlled self-organization of polymer nanopatterns over large areas.

Self-assembly methods allow to obtain ordered patterns on surfaces with exquisite precision, but often lack in effectiveness over large areas. Here we report on the realization of hierarchically ordered polymethylmethacrylate (PMMA) nanofibres and nanodots over large areas from solution via a fast, easy and low-cost method named ASB-SANS, based on a ternary solution that is cast on the substrate. Simple changes to the ternary solution composition allow to control the transition from nanofibres to nanodots, via a wide range of intermediate topologies. The ternary solution includes the material to be patterned, a liquid solvent and a solid substance able to sublimate. The analysis of the fibres/dots width and inter-pattern distance variations with respect to the ratio between the solution components suggests that the macromolecular chains mobility in the solidified sublimating substance follows Zimm-like models (mobility of macromolecules in diluted liquid solutions). A qualitative explanation of the self-assembly phenomena originating the observed nanopatterns is given. Finally, ASB-SANS-generated PMMA nanodots arrays have been used as lithographic masks for a silicon substrate and submitted to Inductively Coupled Plasma-Reactive Ion Etching (ICP-RIE). As a result, nanopillars with remarkably high aspect ratios have been achieved over areas as large as several millimeters square, highlighting an interesting potential of ASB-SANS in practical applications like photon trapping in photovoltaic cells, surface-enhanced sensors, plasmonics.

Easy fabrication of aligned PLLA nanofibers-based 2D scaffolds suitable for cell contact guidance studies.

An easy, low-cost and fast wet processing-based method named ASB-SANS (Auxiliary Solvent-Based Sublimation-Aided NanoStructuring) has been used to fabricate poly(l-lactic acid) (PLLA) highly ordered and hierarchically organized 2D fibrillar patterns, with fiber widths between 40 and 500 nm and lengths exceeding tens of microns. A clear contact guidance effect of these nanofibrillar scaffolds with respect to HeLa and NIH-3T3 cells growth has been observed, on top of an overall good viability. For NIH-3T3 pronounced elongation of the cells was observed, as well as a remarkable ability of the patterns to guide the extension of pseudopodia. Moreover, SEM imaging revealed filopodia stemming from both sides of the pseudopodia and aligned with the secondary PLLA nanofibrous structures created by the ASB-SANS procedure. These results validate ASB-SANS as a technique capable to provide biocompatible 2D nanofibrillar patterns suitable for studying phenomena of contact guidance (and, more in general, the behavior of cells onto nanofibrous scaffolds), at very low costs and in an extremely easy way, accessible to virtually any laboratory.

Luminophores and Carbon Nanotubes: An Odd Combination?

Studies on the exohedral and endohedral functionalization of carbon nanotubes (CNTs) with organic or inorganic chromophores and luminophores have increased substantially in recent years, making use of covalent, supramolecular, electrostatic, and host-guest preparative strategies. Research in this field has fundamental interest because the mixing of two radically different components (molecule/metal complex versus CNT) typically affords materials with exceptional electronic and structural properties while also offering the possibility of studying in detail the interactions between molecules/complexes and nanomaterials. Application perspectives can be also envisaged, particularly in the areas of light-to-electricity (e.g., photovoltaics) and electricity-to-light (e.g., electroluminescence) conversion. Here, we focus in particular on some recent results obtained in the preparation of luminescent hybrids in which suitably designed emitting moieties, placed inside or outside of carbon nanotubes through noncovalent interactions, can afford brightly glowing black photoluminescent nanostructures.

Capturing the geometry of the emissive state of a Cu(I) red emitter through strong intramolecular stacking forces.

Condensation of ethylenediamine with fluorenone produces a diimine with two terminal fluorophores and a flexible central backbone, N,N'-bis-fluoren-9-ylidene-ethane-1,2-diamine (flen). The diimine reacts with [Cu(MeCN)(4)]BF(4) or CuI to produce a homoleptic compound of the stoichiometry [Cu(flen)(2)]BF(4) or [Cu(flen)(2)][CuI(2)] respectively. Both complexes emit in the red part of the spectrum, with a maximum around 720 nm and excited state lifetime of 0.2 µs in solution. The crystal structures of the complexes reveal almost an identical Cu(i)-diimine core where the predominant forces are the intramolecular π-π interactions between the fluorenone aromatic systems resulting in considerably distorted coordination environments. The negligible difference in the emission maximum between solution and solid state indicates that the vibrationally relaxed excited state, assigned as MLCT/IL, adopts a structure closely similar to the crystallographically determined one.

A stable and strongly luminescent dinuclear Cu(I) helical complex prepared from 2-diphenylphosphino-6-methylpyridine.

Treatment of 2-diphenylphosphino-6-methylpyridine (dpPyMe) with Cu(CH(3)CN)(4)BF(4) afforded the stable dinuclear Cu(I) complex [Cu(2)(µ-dpPyMe)(3)(CH(3)CN)](BF(4))(2). This compound is a weak emitter in solution, however a remarkably high emission quantum yield (46%) has been found in a rigid matrix at room temperature.

Electrostatically-driven assembly of MWCNTs with a europium complex.

Luminescent carbon-based materials have been prepared by electrostatic self-assembly of negatively-charged luminescent Eu(III)-complex with imidazolium-functionalized MWCNTs.