Publications by authors named "John Mohanraj"

Nonstoichiometric nickel oxide (NiO) 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 NiO 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.

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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.

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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.

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Unlike the conventional p-doping of organic semiconductors (OSCs) using acceptors, here, an efficient doping concept for diketopyrrolopyrrole-based polymer PDPP[T] -EDOT (OSC-1) is presented using an oxidized p-type semiconductor, Spiro-OMeTAD(TFSI) (OSC-2), exploiting electron transfer from HOMO to HOMO . A shift of work function toward the HOMO upon doping is confirmed by ultraviolet photoelectron spectroscopy (UPS). Detailed X-ray photoelectron spectroscopy (XPS) and UV-vis-NIR absorption studies confirm HOMO to HOMO electron transfer.

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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.

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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.

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The dyads 1-3 made of an alkynylated Zn -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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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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.

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

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