Infrared investigations of 4-hydroxycyanobenzene single crystals

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. © 2013 American Chemical Society.