J-type Coupling Research Articles

Bright and Fast Emission from Robust Supramolecular J-Aggregate Nanostructures through Silica-Encapsulation.

We introduce a two-step silica-encapsulation procedure to optimize both the optical efficiency and structural robustness of 5,5',6,6'-tetrachloro-1,1'-diethyl-3,3'-di(4-sulfobutyl)-benzimidazolocarbocyanine (TDBC), a two-dimensional sheet-like J-aggregate. We report a fluorescence quantum yield of ∼98%, the highest quantum yield recorded for any J-aggregate structure at room temperature, and a fast, emissive lifetime of 234 ps. Silica, as an encapsulating matrix, provides optical transparency, chemical inertness, and robustness to dilution, while rigidifying the J-aggregate structure. Our in situ encapsulation process preserves the excitonic structure in TDBC J-aggregates, maintaining their light absorption and emission properties. The homogeneous silica coating has an average thickness of 0.5-1 nm around J-aggregate sheets. Silica encapsulation permits extensive dilutions of J-aggregates without significant disintegration into monomers. The narrow absorbance and emission line widths exhibit further narrowing upon cooling to 79 K, which is consistent with J-type coupling in the encapsulated aggregates. This silica TDBC J-aggregate construct signifies (1) a bright, fast, and robust fluorophore system, (2) a platform for further manipulation of J-aggregates as building blocks for integration with other optical materials and structures, and (3) a system for fundamental studies of exciton delocalization, transport, and emission dynamics within a rigid matrix.

Slip‐Stacked J‐Aggregate Materials for Organic Solar Cells and Photodetectors (Adv. Mater. 22/2022)

Organic Photovoltaics Slip-stacked J-aggregate materials feature unique optical and electronical properties for organic solar cells and photodetectors, requiring either broad- or narrowband absorbance. In article number 2104678, Frank Würthner and co-workers classify different cases of J-type coupling for different classes of dyes and correlate their optical properties with their characteristic packing arrangements.

Vibrations Responsible for Luminescence from HJ-Aggregates of Conjugated Polymers Identified by Cryogenic Spectroscopy of Single Nanoparticles.

A single polymer chain can be thought of as a covalently bound J-aggregate, where the microscopic transition-dipole moments line up to emit in phase. Packing polymer chains into a bulk film can result in the opposite effect, inducing H-type coupling between chains. Cofacial transition-dipole moments oscillate out of phase, canceling each other out, so that the lowest-energy excited state turns dark. H-aggregates of conjugated polymers can, in principle, be coaxed into emitting light by mixing purely electronic and vibronic transitions. However, it is challenging to characterize this electron-phonon coupling experimentally. In a bulk film, many different conformations exist with varying degrees of intrachain J-type and interchain H-type coupling strengths, giving rise to broad and featureless aggregate absorption and emission spectra. Even if single nanoparticles consisting of only a few single chains are grown in a controlled fashion, the luminescence spectra remain broad, owing to the underlying molecular dynamics and structural heterogeneity at room temperature. At cryogenic temperatures, emission from H-type aggregates should be suppressed because, in the absence of thermal energy, internal conversion drives the aggregate to the lowest-energy dark state. At the same time, electronic and vibronic transitions narrow substantially, facilitating the attribution of spectral signatures to distinct vibrational modes. We demonstrate how to distinguish signatures of interchain H-type aggregate species from those of intramolecular J-type coupling. Whereas all dominant vibronic modes revealed in the photoluminescence (PL) and surface-enhanced resonance Raman scattering spectra of a single chromophore within a single polymer chain are identified in the J-type aggregate luminescence spectra, they are not all present at once in the H-type spectra. Universal spectral features are found for the luminescence from strongly HJ-coupled chains, clearly resolving the vibrations responsible for the nonadiabatic excited-state molecular dynamics that enable light emission. We discuss the possible combinations of vibrational modes responsible for H-type aggregate PL and demonstrate that only one, mainly the lowest energy one, of the three dominant vibrational modes contributes to the 0-1 transition, whereas combinations of all three are found in the 0-2 transition. From this analysis, we can distinguish between energy shifts due to either J-type intrachain coupling or H-type interchain interactions, offering a means to directly discriminate between structural and energetic disorder.

Double J-Coupling Strategy for Near Infrared Emitters.

Fluorophores emitting in the near-infrared (NIR) are highly desired for various applications, but increasing nonradiative rates cause severe fluorescence quenching for wavelengths beyond 800 nm. Here, a bis(squaraine) dye is reported that bears two NIR dyes in a head-to-tail chromophore arrangement. This arrangement leads to intramolecular J-type exciton coupling, resulting in an absorption maximum at 961 nm and a fluorescence peak at 971 nm with a quantum yield of 0.33% in chloroform. In less polar toluene, the bis(squaraine) self-assembles into nanofibers, affording another bathochromic shift with an absorption maximum at 1095 nm and a fluorescence peak at 1116 nm originating from intermolecular J-type coupling.

Unraveling the Contribution of Residual Monomer to the Emission Spectra of Poly(3-hexylthiophene) Aggregates: Implications for Identifying H- and J-type Coupling.

Poly(3-hexylthiophene) (P3HT) is a well-studied benchmark system for semiconducting polymers used in optoelectronic devices. In these materials, aggregation can improve charge transport efficiency or enhance emission yields depending on the interchain packing. This may be inferred from the absorption and emission spectra when analyzed using exciton coupling models such as the well-known H- and J-coupling model of Kasha. The more recently developed weakly coupled H-aggregate (WCH) model quantifies the degree of disorder via the ratio of the electronic origin intensity to that of the first vibronic band. Here, the underlying assumptions of this approach are tested experimentally for P3HT aggregates formed by solvent poisoning using bulk and single-molecule-based spectroscopic techniques. Specifically, we show that the contribution of residual monomeric chains to the aggregate spectrum must be accounted for to properly assign the spectra as H- or J-type. A modification of the WCH model is introduced to account for multiple emissive species.

Solvent Induced Helix Folding of Defined Indolenine Squaraine Oligomers.

A protecting group strategy was employed to synthesise a series of indolenine squaraine dye oligomers up to the nonamer. The longer oligomers show a distinct solvent dependence of the absorption spectra, that is, either a strong blue shift or a strong red shift of the lowest energy bands in the near infrared spectral region. This behaviour is explained by exciton coupling theory as being due to H‐ or J‐type coupling of transition moments. The H‐type coupling is a consequence of a helix folding in solvents with a small Hansen dispersity index. DOSY NMR, small angle neutron scattering (SANS), quantum chemical and force field calculations agree upon a helix structure with an unusually large pitch and open voids that are filled with solvent molecules, thereby forming a kind of clathrate. The thermodynamic parameters of the folding process were determined by temperature dependent optical absorption spectra.

A mechanochromic luminescent material with aggregation-induced emission: Application for pressure sensing and mapping.

In this study, we report a new compound, (E)-4-(((2-hydroxynaphthalen-1-yl)methylene)amino)-3-methylbenzoic acid (HNMB), which shows aggregation-induced emission property as well as intramolecular charge transfer (ICT) nature. In addition, it exhibits unique mechanochromic luminescence (MCL). The HNMB solid powder emits strong emission but shows quenching effect together with bathochromic-shift after grinding, suggesting a high contrast ratio up to 1420%. Through crystallographic analysis, the relationship between MCL nature and molecular packing mode is verified: Molecules in crystalline phase adopt the J-type coupling based on less overlapped π⋯π stacking, in which multiple intermolecular interactions mainly including C-H⋯π, C-H⋯O and hydrogen bonding, help to stabilize such packing mode. When these interactions are destructed by mechanical force, the packing would be disassembled, activating the MCL behavior. Such working mechanism only needs weak external force capable of destructing intermolecular interactions, rendering the MCL material highly sensitive to pressure. As a practical application, a film sensor for pressure detection is designed based on HNMB, which gives a linear relation between the emission intensity and the external pressure in a lower range. The detection limit of the film sensor is 27.24 Mpa, suggesting high sensitivity. In addition, pressure mapping with high contrast ratio is obtained by surface plot, making this pressure sensor a reliable candidate to be instrumented for various applications.

Switching between H- and J-type electronic coupling in single conjugated polymer aggregates

The aggregation of conjugated polymers and electronic coupling of chromophores play a central role in the fundamental understanding of light and charge generation processes. Here we report that the predominant coupling in isolated aggregates of conjugated polymers can be switched reversibly between H-type and J-type coupling by partially swelling and drying the aggregates. Aggregation is identified by shifts in photoluminescence energy, changes in vibronic peak ratio, and photoluminescence lifetime. This experiment unravels the internal electronic structure of the aggregate and highlights the importance of the drying process in the final spectroscopic properties. The electronic coupling after drying is tuned between H-type and J-type by changing the side chains of the conjugated polymer, but can also be entirely suppressed. The types of electronic coupling correlate with chain morphology, which is quantified by excitation polarization spectroscopy and the efficiency of interchromophoric energy transfer that is revealed by the degree of single-photon emission.

Exciton Coupling of Merocyanine Dyes from H- to J-type in the Solid State by Crystal Engineering.

A key issue for the application of π-conjugated organic molecules as thin film solid-state materials is the packing structure, which drastically affects optical and electronic properties due to intermolecular coupling. In this regard, merocyanine dyes usually pack in H-coupled antiparallel arrangements while structures with more interesting J-type coupling have been rarely reported. Here we show that for three highly dipolar merocyanine dyes, which exhibit the same π-scaffold and accordingly equal properties as monomers in solution, the solid-state packing can be changed by a simple variation of aliphatic substituents to afford narrow and intense absorption bands with huge hypsochromic (H) or bathochromic (J) shifts for their thin films and nanocrystals. Time-dependent density functional theory calculations show that the energetic offset of almost 1 eV magnitude results from distinct packing motifs within the crystal structures that comply with the archetype H- or J-aggregate structures as described by Kasha's exciton theory.

Designer Spin Pseudomolecule Implemented with Trapped Ions in a Magnetic Gradient

We report on the experimental investigation of an individual pseudomolecule using trapped ions with adjustable magnetically induced J-type coupling between spin states. Resonances of individual spins are well separated and are addressed with high fidelity. Quantum gates are carried out using microwave radiation in the presence of thermal excitation of the pseudomolecule's vibrations. Demonstrating controlled-NOT gates between non-nearest neighbors serves as a proof-of-principle of a quantum bus employing a spin chain. Combining advantageous features of nuclear magnetic resonance experiments and trapped ions, respectively, opens up a new avenue toward scalable quantum information processing.

Synthesis and analysis of UV/visible spectra of carbocyanine dimer models

Dimers 1 and 2, having a pair of the carbocyanine moieties connected at the meso-positions by an –O–Ph–O– or –S–Ph–S– bridge, were prepared. Their UV/visible spectra displayed a first absorption maxima at ca. 750 nm, a second absorption maxima at ca. 800 nm and a shoulder at ca. 850 nm. Since MOPAC calculations indicated that the configuration of the dimers was folded, but twisted, strong H-type coupling together with weaker J-type coupling takes place along the longer axis of the dimers. The UV/visible spectra of the dimers were characterized by a split in the long wavelength absorption of the corresponding carbocyanine chromophore into a more intense blue shift and a less intense red shift. Remarkably, the dimers showed greater sensitivity to solvent polarity than the monomers 3 and 4.