Influence of Polyfluorinated Side Chains and Soft-Template Method on the Surface Morphologies and Hydrophobic Properties of Electrodeposited Films from Fluorene Bridged Dicarbazole Monomers.

A clear case of relationship between the monomer molecular structure and the capability of tuning the morphology of electrodeposited gas bubbles template polymer thin films is shown. To this end, a series of fluorene-bridged dicarbazole derivatives containing either linear or terminally branched polyfluorinated side chains connected to the fluorene subunit were synthesized and their electrochemical properties were investigated. The new compounds underwent electrochemical polymerization over indium tin oxide electrodes to give hydrophobic films with nanostructural and morphological properties strongly dependent on the nature of the side chains. Gas bubbles templated electropolymerization was next achieved by the addition of tiny amounts of water to the monomer solutions, without using surfactants. Within the investigated set of molecules, the nanostructural properties of the soft-templated films obtained from monomers bearing linear side chains could be fine-tuned by adjusting electrochemical parameters, leading to superhydrophobic surfaces.

Asymmetrically Substituted 10H,10'H-9,9'-Spirobi[acridine] Derivatives as Hole-Transporting Materials for Perovskite Solar Cells.

Hole-transporting materials (HTMs) based on the 10H, 10'H-9,9'-spirobi [acridine] core (BSA50 and BSA51) were synthesized, and their electronic properties were explored. Experimental and theoretical studies show that the presence of rigid 3,6-dimethoxy-9H-carbazole moieties in BSA 50 brings about improved hole mobility and higher work function compared to bis(4-methoxyphenyl)amine units in BSA51, which increase interfacial hole transportation from perovskite to HTM. As a result, perovskite solar cells (PSCs) based on BSA50 boost power conversion efficiency (PCE) to 22.65 %, and a PSC module using BSA50 HTM exhibits a PCE of 21.35 % (6.5×7 cm) with a Voc of 8.761 V and FF of 79.1 %. The unencapsulated PSCs exhibit superior stability to devices employing spiro-OMeTAD, retaining nearly 90 % of their initial efficiency after 1000 h operation output. This work demonstrates the high potential of molecularly engineered spirobi[acridine] derivatives as HTMs as replacements for spiro-OMeTAD.

Polariton condensation in an organic microcavity utilising a hybrid metal-DBR mirror.

We have developed a simplified approach to fabricate high-reflectivity mirrors suitable for applications in a strongly-coupled organic-semiconductor microcavity. Such mirrors are based on a small number of quarter-wave dielectric pairs deposited on top of a thick silver film that combine high reflectivity and broad reflectivity bandwidth. Using this approach, we construct a microcavity containing the molecular dye BODIPY-Br in which the bottom cavity mirror is composed of a silver layer coated by a SiO2 and a Nb2O5 film, and show that this cavity undergoes polariton condensation at a similar threshold to that of a control cavity whose bottom mirror consists of ten quarter-wave dielectric pairs. We observe, however, that the roughness of the hybrid mirror-caused by limited adhesion between the silver and the dielectric pair-apparently prevents complete collapse of the population to the ground polariton state above the condensation threshold.

Spatial Charge Separation as the Origin of Anomalous Stark Effect in Fluorous 2D Hybrid Perovskites.

2D hybrid perovskites (2DP) are versatile materials, whose electronic and optical properties can be tuned through the nature of the organic cations (even when those are seemingly electronically inert). Here, it is demonstrated that fluorination of the organic ligands yields glassy 2DP materials featuring long-lived correlated electron-hole pairs. Such states have a marked charge-transfer character, as revealed by the persistent Stark effect in the form of a second derivative in electroabsorption. Modeling shows that electrostatic effects associated with fluorination, combined with the steric hindrance due to the bulky side groups, drive the formation of spatially dislocated charge pairs with reduced recombination rates. This work enriches and broadens the current knowledge of the photophysics of 2DP, which will hopefully guide synthesis efforts toward novel materials with improved functionalities.

Zinc phthalocyanines as light harvesters for SnO2-based solar cells: a case study.

SnO2 nanoparticles have been synthesized and used as electron transport material (ETM) in dye sensitized solar cells (DSSCs), featuring two peripherally substituted push-pull zinc phthalocyanines (ZnPcs) bearing electron donating diphenylamine substituents and carboxylic acid anchoring groups as light harvesters. These complexes were designed on the base of previous computational studies suggesting that the integration of secondary amines as donor groups in the structure of unsymmetrical ZnPcs might enhance photovoltaics performances of DSSCs. In the case of TiO2-based devices, this hypothesis has been recently questioned by experimental results. Herein we show that the same holds for SnO2, despite the optimal matching of the optoelectronic characteristics of the synthesized nanoparticles and diphenylamino-substituted ZnPcs, thus confirming that other parameters heavily affect the solar cells performances and should be carefully taken into account when designing materials for photovoltaic applications.

BODIPY Dyes Bearing Multibranched Fluorinated Chains: Synthesis, Structural, and Spectroscopic Studies.

A small series of boron-dipyrromethene (BODIPY) dyes, characterized by the presence of multibranched fluorinated residues, were designed and synthesized. The dyes differ in both the position (para-perfluoroalkoxy-substituted phenyl ring or boron functionalization) and number of magnetically equivalent fluorine atoms (27 or 54 fluorine atoms per molecule). Photophysical and crystallographic characterization of the synthesized BODIPYs was carried out to evaluate the effect of the presence of highly fluorinated moieties on the optical and morphological properties of such compounds.

Fluorination of Organic Spacer Impacts on the Structural and Optical Response of 2D Perovskites.

Low-dimensional hybrid perovskites have triggered significant research interest due to their intrinsically tunable optoelectronic properties and technologically relevant material stability. In particular, the role of the organic spacer on the inherent structural and optical features in two-dimensional (2D) perovskites is paramount for material optimization. To obtain a deeper understanding of the relationship between spacers and the corresponding 2D perovskite film properties, we explore the influence of the partial substitution of hydrogen atoms by fluorine in an alkylammonium organic cation, resulting in (Lc)2PbI4 and (Lf)2PbI4 2D perovskites, respectively. Consequently, optical analysis reveals a clear 0.2 eV blue-shift in the excitonic position at room temperature. This result can be mainly attributed to a band gap opening, with negligible effects on the exciton binding energy. According to Density Functional Theory (DFT) calculations, the band gap increases due to a larger distortion of the structure that decreases the atomic overlap of the wavefunctions and correspondingly bandwidth of the valence and conduction bands. In addition, fluorination impacts the structural rigidity of the 2D perovskite, resulting in a stable structure at room temperature and the absence of phase transitions at a low temperature, in contrast to the widely reported polymorphism in some non-fluorinated materials that exhibit such a phase transition. This indicates that a small perturbation in the material structure can strongly influence the overall structural stability and related phase transition of 2D perovskites, making them more robust to any phase change. This work provides key information on how the fluorine content in organic spacer influence the structural distortion of 2D perovskites and their optical properties which possess remarkable importance for future optoelectronic applications, for instance in the field of light-emitting devices or sensors.

Water-Repellent Low-Dimensional Fluorous Perovskite as Interfacial Coating for 20% Efficient Solar Cells.

Hybrid perovskite solar cells have been capturing an enormous research interest in the energy sector due to their extraordinary performances and ease of fabrication. However, low device lifetime, mainly due to material and device degradation upon water exposure, challenges their near-future commercialization. Here, we synthesized a new fluorous organic cation used as organic spacer to form a low-dimensional perovskite (LDP) with an enhanced water-resistant character. The LDP is integrated with three-dimensional (3D) perovskite absorbers in the form of MA0.9FA0.1PbI3 (FA = NH2CH = NH2+, MA = CH3NH3+) and Cs0.1FA0.74MA0.13PbI2.48Br0.39. In both cases, a LDP layer self-assembles as a thin capping layer on the top of the 3D bulk, making the perovskite surface hydrophobic. Our easy and robust approach, validated for different perovskite compositions, limits the interface deterioration in perovskite solar cells yielding to >20% power conversion efficient solar cells with improved stability, especially pronounced in the first hours of functioning under environmental conditions. As a consequence, single and multijunction perovskite devices, such as tandem solar cells, can benefit from the use of the waterproof stabilization here demonstrated, a concept which can be further expanded in the perovskite optoelectronic industry beyond photovoltaics.

Dye-sensitized solar cells based on a push-pull zinc phthalocyanine bearing diphenylamine donor groups: computational predictions face experimental reality.

Computational studies have suggested that the integration of secondary amine as donor groups in the structure of unsymmetrical zinc phthalocyanine (ZnPc) should have positive effects on photovoltaic performance, once the molecule is integrated as light harvester in dye sensitized solar cells (DSSCs). Aiming at obtaining experimental confirmation, we synthesized a peripherally substituted push-pull ZnPc bearing three electron donating diphenylamine substituents and a carboxylic acid anchoring group and integrated it as sensitizer in TiO2-based DSSCs. Detailed functional characterization of solar energy converting devices resulted in ruling out the original hypothesis. The causes of this discrepancy have been highlighted, leading to a better understanding of the conditions for an effective design of push-pull diarylamino substituted ZnPcs for DSSCs.

Femtosecond Charge-Injection Dynamics at Hybrid Perovskite Interfaces.

With a power conversion efficiency (PCE) exceeding 22 %, perovskite solar cells (PSCs) have thrilled photovoltaic research. However, the interface behavior is still not understood and is a hot topic of research: different processes occur over a hierarchy of timescales, from femtoseconds to seconds, which makes perovskite interface physics intriguing. Herein, through femtosecond transient absorption spectroscopy with spectral coverage extending into the crucial IR region, the ultrafast interface-specific processes at standard and newly molecularly engineered perovskite interfaces in state-of-the-art PSCs are interrogated. Ultrafast interfacial charge injection occurs with a time constant of 100 fs, resulting in hot transfer from energetic charges and setting the timescale for the first step involved in the complex charge-transfer process. This is also true for 20 % efficient devices measured under real operation, for which the femtosecond injection is followed by a slower picosecond component. These findings provide compelling evidence for the femtosecond interfacial charge-injection step and demonstrate a robust method for the straightforward identification of interfacial non-equilibrium processes on the ultrafast timescale.

The Role of Ligand Topology in the Decomplexation of Luminescent Lanthanide Complexes by Dipicolinic Acid.

In this study, we present the aqueous solution behavior of two luminescent lanthanide antenna complexes (Eu3+ ⊂1, Dy3+ ⊂9) with different ligand topologies in the presence of dipicolinic acid (DPA, pyridine-2,6-dicarboxylic acid). Macrocyclic (1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid, DO3A, 9) and acyclic (1,4,7-triazaheptane-1,1,7,7-tetraacetic acid, DTTA, 1) ligands have been selected to form a ratiometric pair in which Dy3+ ⊂9 acts as a reference and Eu3+ ⊂1 acts as a probe for the recognition of DPA. The pair of luminescent complexes in water reveals the capability to work as a DPA luminescent sensor. The change of emission intensity of Eu3+ indicates the occurrence of a new sensitization path for the lanthanide cation through excitation of DPA. NMR evidence implies the presence of free 1 and mass spectrometry shows the formation of emitting [EuDPA2 ]- as a result of a ligand exchange reaction.

Efficient luminescence from fluorene- and spirobifluorene-based lanthanide complexes upon near-visible irradiation.

We describe herein the synthesis and photophysical characterization of new lanthanide complexes that consist of a (9,9-dimethylfluoren-2-yl)-2-oxoethyl or a (9,9'-spirobifluoren-2-yl)-2-oxoethyl unit as the antenna, covalently linked to a 1,4,7,10-tetraazacyclododecane-1,4,7-triacetic acid (DO3A) unit as the Ln(3+) (Gd(3+), Eu(3+), Sm(3+), Tb(3+), Dy(3+)) coordination site. We were able to translate the spectroscopic properties of the innovative bipartite ligands into the formation of highly luminescent europium complexes that exhibit efficient emission (ϕ(se)>0.1) upon sensitization in the near-visible region, that is, with an excitation wavelength above 350 nm. The luminescence of the Eu(3+) complexes is clearly detectable at concentrations as low as 10 pM. Furthermore, the structural organization of these bipartite ligands makes the complexes highly soluble in aqueous solutions and chemically stable over time.

Synthesis and photovoltaic applications of a 4,4'-spirobi[cyclopenta[2,1-b;3,4-b']dithiophene]-bridged donor/acceptor dye.

A new donor/acceptor (D-A) spiro dye (SCPDT1) featuring two bithiophene units, connected through an sp(3)-hybridized carbon atom, was prepared by a multistep synthetic sequence involving the convenient assembly of the spiro system under mild catalytic conditions. The photocurrent spectrum of dye-sensitized solar cells incorporating SCPDT1 covers the spectral region ranging from 350 to 700 nm and reaches a wide maximum of ~80% in the 420-560 nm range. Power conversion efficiencies of up to 6.02% were obtained.

A highly sensitive luminescent lectin sensor based on an α-D-mannose substituted Tb3+ antenna complex.

Lectin-carbohydrate interactions are the basis of many biological processes and essentially they constitute the language through which intercellular communications are codified. Thus they represent powerful tools in the examination and interpretation of changes that occur on cell surfaces during both physiological and, more importantly, pathological events. The development of optical techniques that exploit the unique properties of luminescent lanthanoid metal complexes in the investigation of lectin-carbohydrate recognition can foster research in the field of ratiometric biosensing and disease detection. Here we report the synthesis of a Tb(3+)-DO3A complex (Tb⊂1) bearing an α-D-mannose residue and the related study of binding affinity with concanavalin A (Con A) labeled with rhodamine-B-isothiocyanate (RITC-Con A). Luminescence spectroscopy and dynamic studies show changes in emission spectra that can be ascribed to a luminescence resonance energy transfer (LRET) from Tb⊂1 (donor) to RITC-Con A (acceptor). The binding constant value between the two species was found to be one order of magnitude larger than those previously reported for similar types of recognition. To the best of our knowledge this is the first example of the use of a pre-organized luminescent lanthanoid complex in the study of carbohydrate-protein interactions by LRET.

Tuning the nature of the fluorescent state: a substituted polycondensed dye as a case study.

An extensive spectroscopic analysis is presented of an elongated polycondensed dye with a donor-acceptor substitution. The charge-transfer (CT) state, polarized along the long molecular axis, is close in energy to a local excitation (LE) of the polycondensed system, roughly polarized along the short molecular axis, which makes this system particularly suitable to investigate the subtle LE/CT interplay. An essential-state model is presented that quantitatively reproduces absorption and fluorescence spectra, as well as fluorescence emission and excitation anisotropy spectra collected in solvents of different polarity and viscosity, which sets a sound basis for the understanding of how solvent polarity and solvent relaxation affect the nature of low-lying excitations. The markedly different fluorescence emission and excitation anisotropy spectra measured in glassy and liquid polar solvents unambiguously demonstrate the major role played by solvent relaxation in the definition of fluorescence properties of the dye.

New [(D-terpyridine)-Ru-(D or A-terpyridine)][4-EtPhCO2]2 complexes (D = electron donor group; A = electron acceptor group) as active second-order non linear optical chromophores.

The dipolar and octupolar contributions of the second order nonlinear optical properties of [(4'-(C(6)H(4)-p-D)-2,2':6',2''-terpyridine)-Ru-(4'-(C(6)H(4)-p-A)-2,2':6',2''-terpyridine)]Y(2) heteroleptic complexes (D and A are donor and acceptor groups, respectively), and related free terpyridines and homoleptic complexes, have been obtained by means of a comprehensive combination of Electric Field Induced Second Harmonic generation, Third Harmonic Generation, and Harmonic Light Scattering measurements. These results evidence how a metal can act as a bridge between two π-delocalized terpyridine moieties bearing a D and an A group, respectively, leading to a large quadratic hyperpolarizability hugely dominated by the octupolar contribution.

Luminescent Ir(III) complex exclusively made of polypyridine ligands capable of intercalating into calf-thymus DNA.

Efficient intercalation of a luminescent Ir(III) complex exclusively made of polypyridine ligands in natural and synthetic biopolymers is reported for the first time. The emission of the complex is largely enhanced in the presence of [poly(dA-dT)(2)] and strongly quenched in the presence of [poly(dG-dC)(2)]. By comparing the emission decays in DNA and in synthetic polynucleotides, it is proposed that the emission quenching of the title compound by guanine residues in DNA is no longer effective over a distance of four dA-dT base pairs.

Synthesis and photophysical characterization of highly luminescent silica films doped with substituted 2-hydroxyphthalamide (IAM) terbium complexes.

Innovative Tb(3+) antenna complexes employing two different substituted 2-hydroxyphthalamide ligands (HxOH-IAM and bis-HxOH-IAM) acting simultaneously as coordinating sites and light collector units have been synthesized and successively anchored in silica layers by the sol-gel technique. The complexes show remarkable photoluminescence (PL) quantum yields in methanol solution, as high as 0.30 and 0.40 for (HxOH-IAM)(4)⊂Tb(3+) and (bis-HxOH-IAM)(2)⊂Tb(3+), respectively. The grafting of the Tb(3+) complexes in silica single layers accomplished by exploiting the terminal hydroxyl groups of the IAM chains results in highly transparent and homogeneous films displaying bright green emission and PL efficiencies of up to 0.40. The silica layers containing the (bis-HxOH-IAM)(2)⊂Tb(3+) show remarkable photostability even under prolonged and continuous irradiation (up to 3.5 h). The nature of the IAM ligands allows the photoexcitation of the complexes at wavelengths even longer than 350 nm, which is a spectral window suitable to develop luminescent lanthanide probes dedicated to bioanalyses and bioimaging applications.

Polar fluorenes and spirobifluorenes: fluorescence and fluorescence anisotropy spectra.

An extensive spectroscopic study is presented of two asymmetrically substituted fluorene dyes and of the related spiro dimers in both liquid and glassy solvents. Essential-state models are developed to accurately reproduce linear absorption and fluorescence spectra and their complex dependence on solvent polarity. The same models are exploited to quantitatively calculate fluorescence excitation and anisotropy spectra in rigid matrixes. Impressive red-edge effects observed for spiro dimers in glassy polar solvents are accurately reproduced and understood. Interchromophore interactions in the spiro dimers are very small, leading to marginal effects in absorption and fluorescence spectra, but they effectively promote energy transfer between the two chromophores, as best evidenced comparing anisotropy spectra of the substituted fluorenes and of corresponding spiro dimers dissolved in glassy solvent matrixes.