An entry from the Cambridge Structural Database, the world’s repository for small molecule crystal structures. The entry contains experimental data from a crystal diffraction study. The deposited dataset for this entry is freely available from the CCDC and typically includes 3D coordinates, cell parameters, space group, experimental conditions and quality measures.

The anisotropic thermal expansion properties of an organic semiconducting single crystal constituted by 4-hydroxycyanobenzene (4HCB) have been probed by XRD in the range 120-300 K. The anisotropic thermal expansion coefficients for the three crystallographic axes and for the crystal volume have been determined. A careful analysis of the crystal structure revealed that the two different H-bonds stemming from the two independent, differently oriented 4HCB molecules composing the unit cell have different rearrangement patterns upon temperature variations, in terms of both bond length and bond angle. Linearly Polarized Mid InfraRed (LP-MIR) measurements carried out in the same temperature range, focused on the O-H bond spectral region, confirm this finding. The same LP-MIR measurements, on the basis of a semi-empirical relation and of geometrical considerations and assumptions, allowed calculation of the -CNH-O- hydrogen bond length along the a and b axes of the crystal. In turn, the so-calculated -CNH-O- bond lengths were used to derive the thermal expansion coefficients along the corresponding crystal axes, as well as the volumetric one, using just the LP-MIR data. Reasonable to good agreement with the same values obtained from XRD measurements was obtained. This proof-of-principle opens interesting perspectives about the possible development of a rapid, low cost and industry-friendly assessment of the thermal expansion properties of organic semiconducting single crystals (OSSCs) involving hydrogen bonds.

Electronic structure of 4-hydroxycyanobenzene in the gas phase, thick films, and single crystals has been investigated by X-ray photoemission spectroscopy (XPS) and near edge X-ray absorption fine structure spectroscopy (NEXAFS). We have used resonant photoemission spectroscopy (RESPES) to identify the symmetry and atomic localization of the occupied and unoccupied molecular orbitals for the free molecule. Upon condensation into a thick film, we find XPS energy shifts in opposite directions for the oxygen and nitrogen core levels, consistent with the formation of an intermolecular hydrogen bond. This interaction is also accompanied by a significant spatial distortion of the lowest unoccupied molecular orbital that is displaced from the nitrogen atom, as indicated by the RESPES measurements. Thick films and single crystals display the same dichroism in polarization dependent NEXAFS, indicating that the intermolecular hydrogen bonding also steers the molecular assembly into a preferred molecular orientation.

4-Hydroxycyanobenzene (4HCB) single crystals (SCs) and polycrystals (PCs) have been analyzed by means of both unpolarized and linearly polarized (LP) infrared (IR) beams. Most of the signals found at room temperature (298 K) were assigned to well-defined vibrational modes. Using an LP-IR beam and keeping the beam polarization aligned with either the a or the b crystal axis, anisotropic spectra of SCs were also attributed. The differences between the LP and unpolarized spectra of SCs are discussed in view of spatially anisotropic vibronic couplings between the benzenic π electrons and the molecular functional groups (FGs), with reference to the overall lattice arrangement and the polarizability of the FGs. In addition, signals suggesting the low-concentration presence of tautomers within the crystal were detected. LP-IR measurements of SCs in the temperature range between 298 and 120 K are also reported and discussed, with particular reference to the hydrogen-bonding-related functional groups of 4HCB, allowing the assignment of OH bending signals that were otherwise not clearly attributable and the inference of an anisotropic shrinking of the crystals. Overall, the presented results show that LP-IR spectroscopy is a valuable tool for noncontact, nondestructive characterization of organic semiconducting single crystals.

Fingerprints are one the oldest biometrics used in investigations. The fingerprint morphology is considered unique and immutable and it is routinely used to identify an individual from the mark found at the crime scene. The comparison is based solely on the ridges flow and on their discontinuities (i.e. the minutiae), without considering other information possibly embedded in the fingerprint itself. In this work we used a Fourier Transform Infrared microspectroscopy (FT-IRMS) to obtain the morphology and the chemical map of functional groups in fingerprints. The FT-IRMS technique is able to acquire hyperspectral images of the organic compounds present in the samples under examination. However both sophisticated processing and user interaction are required to process the spectra, and no fully automated procedure is currently available. We prepared a set of test fingerprints and collected the data with the FT-IRMS; we then developed an automated procedure to process the data without user interaction and were able to produce maps related to fingerprint deposits. More in details, the developed system is able to produce both integral maps, providing a summary of the contribution in a specific wavelength range, and peak maps, which show the contribution of a selected functional group. The automatic processing steps, although born with the fingerprint in mind, are fairly general, and can be applied to all fields where there is the need to process a large amount of spectra without user interaction.

Forensic science is already taking benefits from synchrotron radiation (SR) sources in trace evidence analysis. In this contribution we show a multi-technique approach to study fingerprints from the morphological and chemical point of view using SR based techniques such as Fourier transform infrared microspectroscopy (FTIRMS), X-ray fluorescence (XRF), X-ray absorption structure (XAS), and phase contrast microradiography. Both uncontaminated and gunshot residue contaminated human fingerprints were deposited on lightly doped silicon wafers and on poly-ethylene-terephthalate foils. For the uncontaminated fingerprints an univariate approach of functional groups mapping to model FT-IRMS data was used to get the morphology and the organic compounds map. For the gunshot residue contaminated fingerprints, after a preliminary elemental analysis using XRF, microradiography just below and above the absorption edge of the elements of interest has been used to map the contaminants within the fingerprint. Finally, XAS allowed us to determine the chemical state of the different elements. The next step will be fusing the above information in order to produce an exhaustive and easily understandable evidence.

Squared, platelet-like single crystals of 4-hydroxycyanobenzene (4HCB) have been grown from solutions based on ethylic ether and petroleum ether. Properly modifying the growth conditions, in terms of both solvent used for the growth and concentration of 4HCB in the starting solution, allowed one to tune the planar dimensions of the platelets in the range 2–6mm, and their thickness in the range 150–600μm. In this way samples well suited for desired practical manipulation and electronic measurements may be obtained. Moreover, lowering the growth temperature resulted in larger but still thin 4HCB crystals. The ability to tailor crystal thickness has allowed one to study their Space-Charge Limited Current (SCLC) behaviour along that dimension, showing that the so-contacted samples exhibit intrinsic-like bulk conduction behaviour, and are hence well suitable for electronic studies and applications.