Chiroptical Properties in Thin Films of π-Conjugated Systems

Chiral π-conjugated molecules provide new materials with outstanding features for current and perspective applications, especially in the field of optoelectronic devices. In thin films, processes such as charge conduction, light absorption, and emission are governed not only by the structure of the individual molecules but also by their supramolecular structures and intermolecular interactions to a large extent. Electronic circular dichroism, ECD, and its emission counterpart, circularly polarized luminescence, CPL, provide tools for studying aggregated states and the key properties to be sought for designing innovative devices. In this review, we shall present a comprehensive coverage of chiroptical properties measured on thin films of organic π-conjugated molecules. In the first part, we shall discuss some general concepts of ECD, CPL, and other chiroptical spectroscopies, with a focus on their applications to thin film samples. In the following, we will overview the existing literature on chiral π-conjugated systems whose thin films have been characterized by ECD and/or CPL, as well other chiroptical spectroscopies. Special emphasis will be put on systems with large dissymmetry factors (gabs and glum) and on the application of ECD and CPL to derive structural information on aggregated states

Impact and amplification of chirality in the aggregation of leucine-appended poly(p-phenylene ethynylene) (PPE)

A leucine-appended poly(p-phenyleneethynylene) (PPE) was prepared in enantiomeric stereoregular (L-1 and D-1) and stereorandom (rac-1) forms. The solution aggregates of L-1, D-1, rac-1, and mixtures of L-1/D-1, were characterized by absorption, electronic circular dichroism and emission spectra. Both rac-1 and L-1/D-1 mixtures are more prone to aggregate than L-1 and D-1. Upon aggregating, the enantiomeric mixtures manifest an apparent majority-rules effect, which is mostly due to the greater tendency to form heterochiral aggregates with respect to homochiral ones. The impact of chirality on the aggregation behaviour of the aminoacid-appended PPE is demonstrated

Circularly polarized light at the mirror: Caveats and opportunities

Moving from the simple concept that reflection onto a mirror surface changes the handedness of circularly polarized light, we describe what happens to the emergent polarization in two different cases after reflection on a back mirror. In the first case, a regular emitter is taken into account, where reflection has the effect to destroy the emergent polarization. In the second case, we show what could happen when a hypothetical apparently non-reciprocal emitting material undergoes a similar experiment. These simple concepts have important implications in the design of efficient circularly polarized emitting devices

Spatially Resolved Chiroptical Spectroscopies Emphasizing Recent Applications to Thin Films of Chiral Organic Dyes

Instrumental techniques able to identify and structurally characterize the aggregation states in thin films of chiral organic π-conjugated materials, from the first-order supramolecular arrangement up to the microscopic and meso-scopic scale, are very helpful for clarifying structure-property relationships. Chiroptical imaging is currently gaining a central role, for its ability of mapping local supramolecular structures in thin films. The present review gives an overview of electronic circular dichroism imaging (ECDi), circularly polarized luminescence imaging (CPLi), and vibrational circular dichroism imaging (VCDi), with a focus on their applications on thin films of chiral organic dyes as case studies

Effective Universal Unrestricted Adversarial Attacks using a MOE Approach

Recent studies have shown that Deep Leaning models are susceptible to adversarial examples, which are data, in general images, intentionally modified to fool a machine learning classifier. In this paper, we present a multi-objective nested evolutionary algorithm to generate universal unrestricted adversarial examples in a black-box scenario. The unrestricted attacks are performed through the application of well-known image filters that are available in several image processing libraries, modern cameras, and mobile applications. The multi-objective optimization takes into account not only the attack success rate but also the detection rate. Experimental results showed that this approach is able to create a sequence of filters capable of generating very effective and undetectable attacks

Production of K∗(892)0 and φ(1020) in pp collisions at √s = 7 TeV

The production of K∗(892)0 and ϕ(1020) in pp collisions at $sqrt{s}=7~mathrm{TeV}$ was measured by the ALICE experiment at the LHC. The yields and the transverse momentum spectra d2 N/dydp T at midrapidity |y|<0.5 in the range

Transfer of Axial Chirality to the Nanoscale Endows Carbon Nanodots with Circularly Polarized Luminescence

We report the synthesis, purification and characterization of chiral carbon nanodots starting from atropoisomeric precursors. The obtained atropoisomeric carbon nanodots are soluble in organic solvents and have good thermal stability, which are desirable features for technological applications. The synthetic protocol is robust, as it supports a number of variations in terms of molecular doping agents. Remarkably, the combination of axially chiral precursors and 1,4-benzoquinone as doping agent results in green-emissive carbon dots displaying circularly polarized luminescence. Dissymmetry factors of |3.5|×10−4 are obtained in solution, without the need of any additional element of chirality. Introducing axial chirality expands the strategies available to tailor the properties of carbon nanodots, paving the way for carbon nanoparticles that combine good processability in organic solvents with engineered advanced chiroptical properties

Chiral Oligothiophenes with Remarkable Circularly Polarized Luminescence and Electroluminescence in Thin Films

We report circular polarized electroluminescence (CPEL) in thin films of self-organized oligothiophenes. Four new 1,4-phenylene and 9H-carbazole-based oligothiophenes were ad hoc designed to ensure efficient spontaneous formation of chiral supramolecular order. They were easily synthetized and their chiroptical properties in thin films were measured. Circularly polarized luminescence (CPL) spectra revealed glum in the order of 10-2 on a wide wavelengths range, originating from their self-organized chiral supramolecular organization. These molecules have reasonable properties as organic semiconductors and for this reason they can constitute the active layer of circularlypolarized organic light-emitting diodes (CP-OLEDs). Thus, we could investigate directly their electroluminescence (EL) and CPEL, without resorting to blends, but rather in a simple multilayer device with basic architecture. This is the first example of a CP-OLED with active layer made only of a small organic compound

Remarkable near-infrared chiroptical properties of chiral Yb, Tm and Er complexes

We carried out a study of absorption (CD) and emission (CPL) chiroptical properties in the NIR region of two sets of Yb, Tm and Er complexes. The two complexes include a D3 symmetric, [TMG-H+]3Ln(BINOLate)3 (Ln = Yb, Tm, Er; TMG = 1,1,3,3-tetramethylguanidine; BINOLate = 1,1'-bi-2-naphtholate), and a tetrakis, C4 symmetric, CsLn(hfbc)4 (Ln = Yb, Tm, Er; hfbc = 3-heptafluorobutylyrylcamphorate). The lanthanides studied gave access to three discrete energy domains, Yb (900-1040 nm), Tm (1180-1240 nm) and Er (1430-1600 nm) in which the chiroptical activity was assessed using gabs (and glum for Yb complexes). Exceptionally high discrimination between left and right circularly polarised light was observed, with values up to almost the theoretical maximum (±2)

Recognition of Cherenkov patterns in high multiplicity environments

An algorithm for the recognition of Cherenkov patterns based on the Hough Transform Method (HTM), modified for signals with intrinsic width in presence of background, is presented. The method basically consists in a mapping of the pad coordinate space directly to the Cherenkov angle parameter space with a crucial increase of performance in the treatment of different pattern shapes and amount of background. The method has been developed in the framework of the ALICE experiment at CERN for the analysis of data taken in the HMPID (High Momentum Particle IDentification) RICH detector prototype test beam