π-Conjugated organic semiconductors have been explored in several optoelectronic devices, yet their use in molecular detection as surface-enhanced Raman spectroscopy (SERS)-active platforms is unknown. Herein, we demonstrate that SERS-active, superhydrophobic and ivy-like nanostructured films of a molecular semiconductor, α,ω-diperfluorohexylquaterthiophene (DFH-4T), can be easily fabricated by vapour deposition. DFH-4T films without any additional plasmonic layer exhibit unprecedented Raman signal enhancements up to 3.4 × 10 for the probe molecule methylene blue. The combination of quantum mechanical computations, comparative experiments with a fluorocarbon-free α,ω-dihexylquaterthiophene (DH-4T), and thin-film microstructural analysis demonstrates the fundamental roles of the π-conjugated core fluorocarbon substitution and the unique DFH-4T film morphology governing the SERS response. Furthermore, Raman signal enhancements up to ∼10 and sub-zeptomole (<10 mole) analyte detection were accomplished by coating the DFH-4T films with a thin gold layer. Our results offer important guidance for the molecular design of SERS-active organic semiconductors and easily fabricable SERS platforms for ultrasensitive trace analysis.
All-optical switching--controlling light with light--has the potential to meet the ever-increasing demand for data transmission bandwidth. The development of organic π-conjugated molecular materials with the requisite properties for all-optical switching applications has long proven to be a significant challenge. However, recent advances demonstrate that polymethine dyes have the potential to meet the necessary requirements. In this review, we explore the theoretical underpinnings that guide the design of π-conjugated materials for all-optical switching applications. We underline, from a computational chemistry standpoint, the relationships among chemical structure, electronic structure, and optical properties that make polymethines such promising materials.
Understanding the relationships between the molecular nonlinear optical (NLO) properties and the bond-length alternation (BLA) or π-bond-order alternation (BOA) along the molecular backbone of linear π-conjugated systems has proven widely useful in the development of NLO organic chromophores and materials. Here, we examine model polymethines to elucidate the reliability of these relationships. While BLA is solely a measure of molecular geometric structure, BOA includes information pertaining to the electronic structure. As a result, BLA is found to be a good predictor of NLO properties only when optimized geometries are considered, whereas BOA is more broadly applicable. Proper understanding of the distinction between BLA and BOA is critical when designing computational studies of NLO properties, especially for molecules in complex environments or in nonequilibrium geometries.
Nanostructured molecular semiconductor films are promising Surface-Enhanced Raman Spectroscopy (SERS) platforms for both fundamental and technological research. Here, we report that a nanostructured film of the small molecule DFP-4T, consisting of a fully π-conjugated diperfluorophenyl-substituted quaterthiophene structure, demonstrates a very large Raman enhancement factor (>105) and a low limit of detection (10−9 M) for the methylene blue probe molecule. This data is comparable to those reported for the best inorganic semiconductor- and even intrinsic plasmonic metal-based SERS platforms. Photoluminescence spectroscopy and computational analysis suggest that both charge-transfer energy and effective molecular interactions, leading to a small but non-zero oscillator strength in the charge-transfer state between the organic semiconductor film and the analyte molecule, are required to achieve large SERS enhancement factors and high molecular sensitivities in these systems. Our results provide not only a considerable experimental advancement in organic SERS figure-of-merits but also a guidance for the molecular design of more sensitive SERS systems.
Quantum mechanical studies of Ag nanoclusters have shown that plasmonic behavior can be modeled in terms of excited states where collectivity among single excitations leads to strong absorption. However, new computational approaches are needed to provide understanding of plasmonic excitations beyond the single-excitation level. We show that semiempirical INDO/CI approaches with appropriately selected parameters reproduce the TD-DFT optical spectra of various closed-shell Ag clusters. The plasmon-like states with strong optical absorption comprise linear combinations of many singly excited configurations that contribute additively to the transition dipole moment, whereas all other excited states show significant cancellation among the contributions to the transition dipole moment. The computational efficiency of this approach allows us to investigate the role of double excitations at the INDO/SDCI level. The Ag cluster ground states are stabilized by slight mixing with doubly excited configurations, but the plasmonic states generally retain largely singly excited character. The consideration of double excitations in all cases improves the agreement of the INDO/CI absorption spectra with TD-DFT, suggesting that the SDCI calculation effectively captures some of the ground-state correlation implicit in DFT. These results provide the first evidence to support the commonly used assumption that single excitations are in many cases sufficient to describe the optical spectra of plasmonic excitations quantum mechanically.
† Electronic supplementary information (ESI) available: Materials and methods, including characterising data for new compounds, details of linear and nonlinear optical characterisation, and theoretical methodology; additional linear spectra, including those for neat chromophore lms; and representative Z-scan spectra. See
Complementary halogen bonding and hydrogen bonding coexist in co-crystals of organoiodines with molecules containing the thioamide functionality. Thiourea.organoiodine co-crystals are shown to exhibit a remarkably reliable synthon with complementary N-H...S ribbons and S...I interactions.
Noble metal nanoclusters containing dozens to hundreds of metal atoms are of great interest because of their unique optical properties. Classical electrodynamics fails to describe the optical properties of clusters smaller than a few nanometers, so quantum-mechanical models are needed to describe these clusters. However, it is challenging to identify which features of the computed excited states indicate plasmon-like character, particularly in a way that is generalizable to the ligand-protected clusters that are commonly studied in experiments. We present an analytical method to identify plasmonlike excited states using three quantifiable indicators that must be considered in combination: (1) large superatomic character, (2) large collectivity among single-particle excitations, and (3) large additivity of contributions of these single-particle excitations to the transition dipole moment. Visualizing these three indicators on a single plot enables rapid classification of hundreds of excited states into plasmon-like, collective, single-particle, or interband categories or as intermediate between these categories. This method is used to identify excited states with plasmon-like character in both bare and ligand-protected Ag clusters at the TDDFT level. Using these three nearly orthogonal indicators in combination provides more information than any one criterion can provide.
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