Collective Mid-Infrared Vibrations in Surface-Enhanced Raman Scattering.

Surface-enhanced Raman scattering (SERS) is typically assumed to occur at individual molecules neglecting intermolecular vibrational coupling. Here, we show instead how collective vibrations from infrared (IR) coupled dipoles are seen in SERS from molecular monolayers. Mixing IR-active molecules with IR-inactive spacer molecules controls the intermolecular separation. Intermolecular coupling leads to vibrational frequency upshifts up to 8 cm-1, tuning with the mixing fraction and IR dipole strength, in excellent agreement with microscopic models and density functional theory. These cooperative frequency shifts can be used as a ruler to measure intermolecular distance and disorder with angstrom resolution. We demonstrate this for photochemical reactions of 4-nitrothiophenol, which depletes the number of neighboring IR-active molecules and breaks the collective vibration, enabling direct tracking of the reaction. Collective molecular vibrations reshape SERS spectra and need to be considered in the analysis of vibrational spectra throughout analytical chemistry and sensing.

Highly Luminescent Encapsulated Narrow Bandgap Polymers Based on Diketopyrrolopyrrole.

We present the synthesis and characterization of a series of encapsulated diketopyrrolopyrrole red-emitting conjugated polymers. The novel materials display extremely high fluorescence quantum yields in both solution (>70%) and thin film (>20%). Both the absorption and emission spectra show clearer, more defined features compared to their naked counterparts demonstrating the suppression of inter and intramolecular aggregation. We find that the encapsulation results in decreased energetic disorder and a dramatic increase in backbone colinearity as evidenced by scanning tunnelling microscopy. This study paves the way for diketopyrrolopyrrole to be used in emissive solid state applications and demonstrates a novel method to reduce structural disorder in conjugated polymers.

Functionalized surface-confined pores: guest binding directed by lateral noncovalent interactions at the solid-liquid interface.

We present here the construction of self-assembled two-dimensional (2D) molecular networks that contain pores equipped with functional groups that promote guest-specific binding at the liquid/solid interface. For this purpose, a dehydrobenzo[12]annulene (DBA) derivative, DBA-F, having perfluoroalkyl groups at the end of the three alternating alkoxy chains connected by para-phenylene linkers was synthesized. For comparison DBA-H, having the same carbon backbone without fluorine substituents, was also prepared. STM observations revealed that these molecules formed porous 2D networks whose pores were decorated with either fluoroalkane or simple alkane perimeters. Hexakis(phenylethynyl)benzene, HPEB, and its octadecafluoro derivative, HPEB-F surrounded by 18 fluorine atoms, were employed as planar guest molecules of suitable size. The fluoroalkane-lined pores present in the network of DBA-F exhibited good binding ability toward both guest molecules via fluorophilicity and electrostatic interaction, respectively. In contrast the binding ability of the alkane-lined pore of the network of DBA-H for the fluorinated guest HPEB-F was poor as a result of weaker electrostatic interaction. Interestingly, with HPEB as a guest, this network underwent a periodical structural deformation through an induced-fit mechanism to form a superlattice structure consisting of free and occupied pores. These observations are discussed based on modeling experiments using molecular mechanics and quantum chemical methods to elucidate the roles of lateral noncovalent interactions and size matching between the pore and the guest molecules used for 2D guest binding.