Nanographene-Based Decoration as a Panchromatic Antenna for Metalloporphyrin Conjugates.

Porphyrins, a type of heterocyclic aromatic compounds consisting of tetrapyrroles connected by four substituted methine groups, are appealing building blocks for solar energy applications. However, their photosensitization capability is limited by their large optical energy gap, which results in a mismatch in absorption toward efficient harvesting of the solar spectrum. Porphyrin π-extension by edge-fusing with nanographenes can be employed for narrowing their optical energy gap from 2.35 to 1.08 eV, enabling the development of porphyrin-based panchromatic dyes with an optimized energy onset for solar energy conversion in dye-sensitized solar fuel and solar cell configurations. By combining time-dependent density functional theory with fs transient absorption spectroscopy, it is found that the primary singlets, which are delocalized across the entire aromatic part, are transferred into metal centred triplets in only 1.2 ps; and subsequently, relax toward ligand-delocalized triplets. This observation implies that the decoration of the porphyrin moiety with nanographenes, while having a large impact on the absorption onset of the novel dye, promotes the formation of a ligand-centred lowest triplet state of large spatial extension, potentially interesting for boosting interactions with electron scavengers. These results reveal a design strategy for broadening the applicability of porphyrin-based dyes in optoelectronics.

Zigzag-Edged Polycyclic Aromatic Hydrocarbons from Benzo[m]tetraphene Precursors.

A series of zigzag-edged polycyclic aromatic hydrocarbons (PAHs) (Z1-Z3) were synthesized from 2,12-dibromo-7,14-diphenyl-benzo[m]tetraphene (9) as a versatile building block. Their structures were unambiguously confirmed by laser desorption/ionization time-of-flight mass spectrometry, 1 H NMR, Raman, and Fourier-transformed infrared (FTIR) spectroscopies as well as scanning tunneling microscopy. The fingerprint vibrational modes were elucidated with theoretical support. The edge- and size-dependent optical properties were characterized by UV-Vis absorption and fluorescence spectroscopy and DFT calculations. Moreover, ultrafast transient absorption spectroscopy revealed distinct modulation of the photophysical properties upon π-extension from Z1 to Z2, the latter having a gulf edge.

Azobenzene photoisomerization probes cell membrane viscosity.

The viscosity of cell membranes is a crucial parameter that affects the diffusion of small molecules both across and within the lipid membrane and that is related to several diseases. Therefore, the possibility to measure quantitatively membrane viscosity on the nanoscale is of great interest. Here, we report a complete investigation of the photophysics of an amphiphilic membrane-targeted azobenzene (ZIAPIN2) and we propose its use as a viscosity probe for cell membranes. We exploit ZIAPIN2 trans-cis photoisomerization to develop a molecular viscometer and to assess the viscosity of Escherichia coli bacteria membranes employing time-resolved fluorescence spectroscopy. Fluorescence lifetime measurements of ZIAPIN2 in E. coli bacteria suspensions correctly indicate that the membrane viscosity decreases as the temperature of the sample increases. Given the non-homogeneity and the anisotropy of cell membranes, as supported by the photophysical characterization of the probe within the lipid bilayer, we shed new light on the intricate membrane rheology.

Excited states engineering enables efficient near-infrared lasing in nanographenes.

The spectral overlap between stimulated emission (SE) and absorption from dark states (i.e. charges and triplets) especially in the near-infrared (NIR), represents one of the most effective gain loss channels in organic semiconductors. Recently, bottom-up synthesis of atomically precise graphene nanostructures, or nanographenes (NGs), has opened a new route for the development of environmentally and chemically stable materials with optical gain properties. However, also in this case, the interplay between gain and absorption losses has hindered the attainment of efficient lasing action in the NIR. Here, we demonstrate that the introduction of two fluoranthene imide groups to the NG core leads to a more red-shifted emission than the precursor NG molecule (685 vs. 615 nm) and also with a larger Stokes shift (45 nm vs. 2 nm, 1026 cm-1vs. 53 cm-1, respectively). Photophysical results indicate that, besides the minimisation of ground state absorption losses, such substitution permits to suppress the detrimental excited state absorption in the NIR, which likely arises from a dark state with charge-transfer character and triplets. This has enabled NIR lasing (720 nm) from all-solution processed distributed feedback devices with one order of magnitude lower thresholds than those of previously reported NIR-emitting NGs. This study represents an advance in the field of NGs and, in general, organic semiconductor photonics, towards the development of cheap and stable NIR lasers.

Anisotropic Complex Refractive Indices of Atomically Thin Materials: Determination of the Optical Constants of Few-Layer Black Phosphorus.

In this work, studies of the optical constants of monolayer transition metal dichalcogenides and few-layer black phosphorus are briefly reviewed, with particular emphasis on the complex dielectric function and refractive index. Specifically, an estimate of the complex index of refraction of phosphorene and few-layer black phosphorus is given. The complex index of refraction of this material was extracted from differential reflectance data reported in the literature by employing a constrained Kramers-Kronig analysis combined with the transfer matrix method. The reflectance contrast of 1-3 layers of black phosphorus on a silicon dioxide/silicon substrate was then calculated using the extracted complex indices of refraction.

The Effect of an Intramembrane Light-Actuator on the Dynamics of Phospholipids in Model Membranes and Intact Cells.

The noncovalent intercalation of amphiphilic molecules in the lipid membrane can be exploited to modulate efficiently the physical status of the membrane. Such effects are largely employed in a range of applications, spanning from drug-delivery to therapeutics. In this context, we have very recently developed an intramembrane photo-actuator consisting of an amphiphilic azobenzene molecule, namely ZIAPIN2. The selective photo-isomerization occurring in the lipid bilayer induces a photo-triggered change in the membrane thickness and capacitance, eventually permitting to evoke light-induced neuronal firing both in vitro and in vivo. Here, we present a study on the dynamical perturbation in the lipid membrane caused by ZIAPIN2 and its vehicle solvent, dimethyl sulfoxide. Effects on the dynamics occurring in the picosecond time range and at the molecular level are probed using quasi-elastic neutron scattering. By coupling experiments carried out both on model membranes and intact cells, we found that DMSO leads to a general retardation of the dynamics within a more dynamically ordered landscape, a result that we attribute to the dehydration at the interface. On the other hand, ZIAPIN2 partitioning produces a general softening of the bilayer owing to its interaction with the lipids. These data are in agreement with our recent studies, which indicate that the efficacy of ZIAPIN2 in triggering cellular signalling stems from its ability to mechanically perturb the bilayer as a whole, by forming light-sensitive membrane spanning dimers.

Dual Amplified Spontaneous Emission and Lasing from Nanographene Films.

Chemically synthesized zigzag-edged nanographenes (NG) have recently demonstrated great success as the active laser units in solution-processed organic distributed feedback (DFB) lasers. Here, we report the first observation of dual amplified spontaneous emission (ASE) from a large-size NG derivative (with 12 benzenoid rings) dispersed in a polystyrene film. ASE is observed simultaneously at the 685 and 739 nm wavelengths, which correspond to different transitions of the photoluminescence spectrum. Ultrafast pump-probe spectroscopy has been used to ascertain the underlying photophysical processes taking place in the films. DFB lasers, based on these materials and top-layer nanostructured polymeric resonators (i.e., one or two-dimensional surface relief gratings), have been fabricated and characterized. Lasers emitting close to either one of the two possible ASE wavelengths, or simultaneously at both of them, have been prepared by proper selection of the resonator parameters.

Integration of bio-responsive silver in 1D photonic crystals: towards the colorimetric detection of bacteria.

The colour purity and versatility of fabrication of one-dimensional photonic crystals (1D PhCs) make them ideal candidates for colorimetric sensing of a variety of analytes. For instance, the detection of bacterial contaminants in food via colorimetric sensors can be highly appealing, as most of the existing detection techniques are in general time-consuming and the read-out requires specialised personnel. Here, we present a colorimetric sensor based on hybrid plasmonic/photonic 1D crystals. We demonstrate that the modification of the silver plasmon resonance brought about by the effective silver/bacterium interaction can be translated into the visible spectral region, producing a change in the structural colour. In addition, we observe a superior colorimetric sensitivity against the Gram negative Escherichia coli compared to the Gram positive Micrococcus luteus, a result that we attribute to the more efficient electrostatic interaction and cellular adhesion between the silver surface and the Gram-negative bacteria outer membrane. This approach demonstrates that in principle an easy colorimetric detection of bacterial contaminants can be achieved through the use of bio-responsive plasmonic materials, such as silver, whose selective electrostatic interaction with bacterial cell wall is well-known and occurs without the need of chemical functionalisation.

Hexa-peri-benzocoronene with two extra K-regions in an ortho-configuration.

There are three possible isomers for hexa-peri-hexabenzocoronene (HBC) with two extra K-regions, but only two of them have been reported, namely with the meta- and para-configurations. Herein, we describe the synthesis of HBC 4 with two extra K-regions in the ortho-configuration, forming a longer zigzag edge compared with the other two isomers. The structure of 4 was validated by laser desorption/ionization time-of-flight mass analysis and nuclear magnetic resonance spectra, as well as Raman and infrared spectroscopies supported by density functional theory calculations. The optical properties of 4 were investigated by UV/vis absorption and ultrafast transient absorption spectroscopy. Together with the analysis of aromaticity, the influence of the zigzag edge on the π-conjugation pathway and HOMO-LUMO gaps of the three isomers were investigated.

π-Extended Pyrene-Fused Double [7]Carbohelicene as a Chiral Polycyclic Aromatic Hydrocarbon.

A π-extended double [7]carbohelicene 2 with fused pyrene units was synthesized, revealing considerable intra- and intermolecular π-π interactions as confirmed with X-ray crystallography. As compared to the previous double [7]carbohelicene 1, the π-extended homologue 2 demonstrated considerably red-shifted absorption with an onset at 645 nm (1: 550 nm) corresponding to a smaller optical gap of 1.90 eV (1: 2.25 eV). A broad near-infrared emission from 600 to 900 nm with a large Stokes shift of ∼100 nm (2.3 × 103 cm-1) was recorded for 2, implying formation of an intramolecular excimer upon excitation, which was corroborated with femtosecond transient absorption spectroscopy. Moreover, 2 revealed remarkable chiral stability with a fairly high isomerization barrier of 46 kcal mol-1, according to density functional theory calculations, which allowed optical resolution by chiral HPLC and suggests potential applications in chiroptical devices.

All-polymer methylammonium lead iodide perovskite microcavities.

Thanks to a high photoluminescence quantum yield, large charge carrier diffusion, and ease of processing from solution, perovskite materials are becoming increasingly interesting for flexible optoelectronic devices. However, their deposition requires wide range solvents that are incompatible with many other flexible and solution-processable materials, including polymers. Here, we show that methylammonium lead iodide (MAPbI3) films can be directly synthesized on all-polymer microcavities via simple addition of a perfluorinated layer which protects the polymer photonic structure from the perovskite processing solvents. The new processing provides microcavities with a quality factor Q = 155, that is in agreement with calculations and the largest value reported so far for fully solution processed perovskite microcavities. Furthermore, the obtained microcavity shows strong spectral and angular redistribution of the the MAPbI3 photoluminescence spectrum, which shows a 3.5 fold enhanced intensity with respect to the detuned reference. The opportunity to control and modify the emission of a MAPbI3 film via a simple spun-cast polymer structure is of great interest in advanced optoelectronic applications requiring high colour purity or emission directionality.

Regioselective Hydrogenation of a 60-Carbon Nanographene Molecule toward a Circumbiphenyl Core.

Regioselective peripheral hydrogenation of a nanographene molecule with 60 contiguous sp2 carbons provides unprecedented access to peralkylated circumbiphenyl (1). Conversion to the circumbiphenyl core structure was unambiguously validated by MALDI-TOF mass spectrometry, NMR, FT-IR, and Raman spectroscopy. UV-vis absorption spectra and DFT calculations demonstrated the significant change of the optoelectronic properties upon peripheral hydrogenation. Stimulated emission from 1, observed via ultrafast transient absorption measurements, indicates potential as an optical gain material.

Room-Temperature Low-Threshold Lasing from Monolithically Integrated Nanostructured Porous Silicon Hybrid Microcavities.

Silicon photonics would strongly benefit from monolithically integrated low-threshold silicon-based laser operating at room temperature, representing today the main challenge toward low-cost and power-efficient electronic-photonic integrated circuits. Here we demonstrate low-threshold lasing from fully transparent nanostructured porous silicon (PSi) monolithic microcavities (MCs) infiltrated with a polyfluorene derivative, namely, poly(9,9-di- n-octylfluorenyl-2,7-diyl) (PFO). The PFO-infiltrated PSiMCs support single-mode blue lasing at the resonance wavelength of 466 nm, with a line width of ∼1.3 nm and lasing threshold of 5 nJ (15 µJ/cm2), a value that is at the state of the art of PFO lasers. Furthermore, time-resolved photoluminescence shows a significant shortening (∼57%) of PFO emission lifetime in the PSiMCs, with respect to nonresonant PSi reference structures, confirming a dramatic variation of the radiative decay rate due to a Purcell effect. Our results, given also that blue lasing is a worst case for silicon photonics, are highly appealing for the development of low-cost, low-threshold silicon-based lasers with wavelengths tunable from visible to the near-infrared region by simple infiltration of suitable emitting polymers in monolithically integrated nanostructured PSiMCs.

Solution processable and optically switchable 1D photonic structures.

We report the first demonstration of a solution processable, optically switchable 1D photonic crystal which incorporates phototunable doped metal oxide nanocrystals. The resulting device structure shows a dual optical response with the photonic bandgap covering the visible spectral range and the plasmon resonance of the doped metal oxide the near infrared. By means of a facile photodoping process, we tuned the plasmonic response and switched effectively the optical properties of the photonic crystal, translating the effect from the near infrared to the visible. The ultrafast bandgap pumping induces a signal change in the region of the photonic stopband, with recovery times of several picoseconds, providing a step toward the ultrafast optical switching. Optical modeling uncovers the importance of a complete modeling of the variations of the dielectric function of the photodoped material, including the high frequency region of the Drude response which is responsible for the strong switching in the visible after photodoping. Our device configuration offers unprecedented tunability due to flexibility in device design, covering a wavelength range from the visible to the near infrared. Our findings indicate a new protocol to modify the optical response of photonic devices by optical triggers only.

Synthesis of Dibenzo[hi,st]ovalene and Its Amplified Spontaneous Emission in a Polystyrene Matrix.

A large number of graphene molecules, or large polycyclic aromatic hydrocarbons (PAHs), have been synthesized and display various optoelectronic properties. Nevertheless, their potential for application in photonics has remained largely unexplored. Herein, we describe the synthesis of a highly luminescent and stable graphene molecule, namely a substituted dibenzo[hi,st]ovalene (DBO 1), with zigzag edges and elucidate its promising optical-gain properties by means of ultrafast transient absorption spectroscopy. Upon incorporation of DBO into an inert polystyrene matrix, amplified stimulated emission can be observed with a relatively low power threshold (ca. 60 µJ cm-2 ), thus highlighting its high potential for lasing applications.