An Investigation of the Requirements for Excimer Formation and Charge Stabilization in Model Pi-Stacked Assemblies

Formation of -stacked excimers plays an important role in many systems, ranging from biological phenomena and polymer formation and function to photovoltaic devices and organic molecular electronics. In these systems, the geometrical reorganization of the ground state upon photoexcitation is still a subject of debate. In this work, we compare the dynamics of excimer formation and hole (charge) stabilization in fluorene and fluorene-based model systems. We use a variety of gas-phase methods to examine the spectroscopy and dynamics of these systems, including Two-Color Resonant Two-Photon Ionization (2CR2PI), Hole-Burning (HB), Laser Induced Fluorescence (LIF), and Dispersed Fluorescence (DF). In order to quantify the clusters’ geometry, minimum, and relative energies, calculations using Density Functional Theory and high level ab initio methods are reported. These techniques were applied to better understand the energetic properties and behaviors of these model systems in their ground (S0), excited (S1), and ionized (M+•) states to probe the geometrical reorganization resulting in excimer formation and stabilization of charge. As model systems, we used fluorene based assemblies that are covalently linked by utilizing methylene or cyclohexane bridges, which connect two or more fluorene sub-units together. These are compared with clusters interacting at the van der Waals contact distance (3.5 Å). It was found that in both covalently linked and vdW bound systems, excimer formation is dominant; however, the excimer state is stabilized by covalent linkage. We also find cases in which the geometric requirements for excimer formation are not met. Almost every system studied displayed the ability to stabilize charge in its ionic state and therefore showed that the requirements necessary to delocalize charge are less stringent than those necessary for excimer formation

On Pi-Stacking, CH/Pi, and Halogen Bonding in Halobenzene Clusters: Resonant 2-Photon Ionization Studies of Chlorobenzene

Noncovalent interactions such as hydrogen bonding, π-π stacking, CH/π interactions, and halogen bonding play crucial roles in a broad spectrum of chemical and biochemical processes, and can exist in cooperation or competition. Here we report studies of the homoclusters of chlorobenzene, a prototypical system where π-π stacking, CH/π interactions, and halogen bonding interactions may all be present. The electronic spectra of chlorobenzene monomer and clusters (Clbz)n with n = 1-4 were obtained using resonant 2-photon ionization in the origin region of the S0–S1 (ππ*) state of the monomer. The cluster spectra show in all cases a broad spectrum whose center is redshifted from the monomer absorption. Electronic structure calculations aid in showing that the spectral broadening arises in large part from inhomogeneous sources, including the presence of multiple isomers and Franck-Condon (FC) activity associated with geometrical changes induced by electronic excitation. Calculations at the M06-2x/aug-cc-pVDZ level find in total five minimum energy structures for the dimer, four π-stacked structures, and one T-shaped, and six representative minimum energy structures were found for the trimer. The calculated time-dependent density functional theory spectra using range-separated and meta-GGA hybrid functionals show that these isomers absorb over a range that is roughly consistent with the breadth of the experimental spectra, and the calculated absorptions are redshifted with respect to the monomer transition, in agreement with experiment. Due to the significant geometry change in the electronic transition, where for the dimer a transition from a parallel displaced to sandwich structure occurs with a reduced separation of the two monomers, significant FC activity is predicted in low frequency intermolecular modes

ELECTRONIC COMMUNICATION IN COVALENTLY vs. NON-COVALENTLY BONDED POLYFLUORENE SYSTEMS: THE ROLE OF THE COVALENT LINKER.

begin{wrapfigure}{l}{0pt} includegraphics[scale=0.14]{Capture.eps} end{wrapfigure} The covalently linked polyfluorene molecules F1-F6 (see left) are prototypical molecular wires by virtue of their favorable electron/hole transport properties brought about by $pi$-stacking. To understand the role of the covalent linker in facilitating electron transport in these systems, we have investigated several van der Waals (vdW) analogues by resonant mass spectroscopy. Electronic spectra and ion yield curves are reported for jet-cooled vdW clusters containing up to six fluorene units. The near-coincidence of the electronic band origins for the dimer and larger clusters suggests that a structure containing a central dimer chromophore is the predominant conformational motif. As for F1-F6, the threshold ionization potentials extracted from the ion yield measurements decrease linearly with inverse cluster size. Importantly, however, the rate of decrease is significantly smaller in the vdW clusters, indicating more efficient hole stabilization in the covalently bound systems. Results for similar vdW clusters that are locked into specific conformations by steric effects will also be reported

Effect of Facial Encumbrance on Excimer Formation and Charge Resonance Stabilization in Model Bichromophoric Assemblies

Excimer formation and charge resonance stabilization in covalently linked bichromophoric systems with flexible spacers are important processes relevant to biochemistry and functional materials. Requiring a π-stacked cofacial arrangement of a pair of aromatic molecules at a van der Waals contact, the underlying geometrical reorganization that accompanies these events continues to be debated. Here we use a variety of methods including two-color resonant two-photon ionization spectroscopy (2CR2PI), ion yield measurements, hole-burning spectroscopy (HB), and laser-induced fluorescence (LIF) excitation and emission spectroscopy to compare the gas-phase spectroscopy and dynamics of the van der Waals dimers of fluorene, 9-methylfluorene (MF), and 9,9′-dimethylfluorene (F1). The goal of this work is to probe the influence of methyl substitution on the dynamics of excimer formation and charge resonance (CR) stabilization. The fluorene dimer, (F)2, displays lifetime broadened electronic spectra and the dominance of excimer emission, consistent with a rapid (picoseconds) formation of a π-stacked excimer upon electronic excitation. Ion yield measurements of (F)2 reveal a lowering of the ionization potential (IP) by some 0.38 eV relative to the monomer, reflecting significant CR stabilization. These trends are mirrored in the 9-methylfluorene dimer, (MF)2, as one face of the π-system remains open. In contrast, the electronic spectrum of the dimethyl-substituted dimer, (F1)2, shows narrow features representing a single band system, and analysis of the torsional structure in dispersed fluorescence spectra identifies this as emission from the locally excited state of a tilted (non-π-stacked) dimer, with no evidence of excimeric emission. The structure of this dimer reflects the increased importance of C–H/π interactions in the dimethyl-substituted system, as increased steric constraints block a cofacial approach. The IP of (F1)2 shows CR stabilization which is roughly 1/2 of that in π-stacked (F)2 dimer. Extensive theoretical calculations support these findings and show the importance of sandwich-type configurations for excitonic delocalization and CR stabilization

First Experimental Evidence for the Diverse Requirements of Excimer vs Hole Stabilization in π-Stacked Assemblies

Exciton formation and charge separation and transport are key dynamical events in a variety of functional polymeric materials and biological systems, including DNA. Beyond the necessary cofacial approach of a pair of aromatic molecules at van der Waals contact, the extent of overlap and necessary geometrical reorganization for optimal stabilization of an excimer vs dimer cation radical remain unresolved. Here, we compare experimentally the dynamics of excimer formation (via emission) and charge stabilization (via threshold ionization) of a novel covalently linked, cofacially stacked fluorene dimer (F2) with the unlinked van der Waals dimer of fluorene, that is, (F)2. Although the measured ionization potentials are identical, the excimeric state is stabilized by up to ∼30 kJ/mol in covalently linked F2. Supported by theory, this work demonstrates for the first time experimentally that optimal stabilization of an excimer requires a perfect sandwich-like geometry with maximal overlap, whereas hole stabilization in π-stacked aggregates is less geometrically restrictive

π-Stacking, C–H/π, and Halogen Bonding Interactions in Bromobenzene and Mixed Bromobenzene–Benzene Clusters

Noncovalent interactions play an important role in many chemical and biochemical processes. Building upon our recent study of the homoclusters of chlorobenzene, where π–π stacking and CH/π interactions were identified as the most important binding motifs, in this work we present a study of bromobenzene (PhBr) and mixed bromobenzene–benzene clusters. Electronic spectra in the region of the PhBr monomer S0–S1 (ππ*) transition were obtained using resonant two-photon ionization (R2PI) methods combined with time-of-flight mass analysis. As previously found for related systems, the PhBr cluster spectra show a broad feature whose center is red-shifted from the monomer absorption, and electronic structure calculations indicate the presence of multiple isomers and Franck–Condon activity in low-frequency intermolecular modes. Calculations at the M06-2X/aug-cc-pVDZ level find in total eight minimum energy structures for the PhBr dimer: four π-stacked structures differing in the relative orientation of the Br atoms (denoted D1–D4), one T-shaped structure (D5), and three halogen bonded structures (D6–D8). The calculated binding energies of these complexes, corrected for basis set superposition error (BSSE) and zero-point energy (ZPE), are in the range of −6 to −24 kJ/mol. Time-dependent density functional theory (TDDFT) calculations predict that these isomers absorb over a range that is roughly consistent with the breadth of the experimental spectrum. To examine the influence of dipole–dipole interaction, R2PI spectra were also obtained for the mixed PhBr···benzene dimer, where the spectral congestion is reduced and clear vibrational structure is observed. This structure is well-simulated by Franck–Condon calculations that incorporate the lowest frequency intermolecular modes. Calculations find four minimum energy structures for the mixed dimer and predict that the binding energy of the global minimum is reduced by 30% relative to the global minimum PhBr dimer structure

Cofacially Arrayed Polyfluorenes: Spontaneous Formation of π-Stacked Assemblies in the Gas Phase

Understanding geometrical and size dependencies of through-space charge delocalization in multichromophoric systems is critical to model electron transfer and transport in materials and biomolecules. In this work, we examine the size evolution of hole delocalization in van der Waals clusters of fluorene (i.e., (F)n), where a range of geometries are possible, reflecting both π-stacking and C–H/π interactions. Using mass-selected two-color resonant two-photon ionization spectroscopy (2CR2PI), we measure electronic spectra and vertical ionization potentials (IPs) in the gas phase. Results are compared with model covalently linked assemblies (denoted Fn), exhibiting a sterically enforced cofacial (i.e., π-stacked) orientation of chromophores. For both systems, an inverse size dependence (i.e., 1/n) of IP vs cluster size is found. Surprisingly, the values for the two sets fall on the same line! This trend is examined via theory, which emphasizes the important role of π-stacking, and its geometrical dependencies, in the process of hole delocalization in multichromophoric assemblies

π-π stacking vs. C–H/π interaction: Excimer formation and charge resonance stabilization in van der Waals clusters of 9,9′-dimethylfluorene

Studies of exciton and hole stabilization in multichromophoric systems underpin our understanding of electron transfer and transport in materials and biomolecules. The simplest model systems are dimeric, and recently we compared the gas-phase spectroscopy and dynamics of van der Waals dimers of fluorene, 9-methylfluorene (MF), and 9,9′-dimethylfluorene (F1) to assess how sterically controlled facial encumbrance modulates the dynamics of excimer formation and charge resonance stabilization (CRS). Dimers of fluorene and MF show only excimer emission upon electronic excitation, and significant CRS as evidenced in a reduced ionization potential for the dimer relative the monomer. By contrast, the dimer of F1 shows no excimeric emission, rather structured emission from the locally excited state of a tilted (non π-stacked) dimer, evidencing the importance of C–H/π interactions and increased steric constraints that restrict a cofacial approach. In this work, we report our full results on van der Waals clusters of F1, using a combination of theory and experiments that include laser-induced fluorescence, mass-selected two-color resonant two-photon ionization spectroscopy, and two-color appearance potential measurements. We use the latter to derive the binding energies of the F1 dimer in ground, excited, and cation radical states. Our results are compared with van der Waals and covalently linked clusters of fluorene to assess both the relative strength of π-stacking and C–H/π interactions in polyaromatic assemblies and the role of π-stacking in excimer formation and CRS

Isoform-specific targeting of PKA to multivesicular bodies

PKA RIα subunit is localized to MVBs by the A-kinase–anchoring protein AKAP11 when disassociated from the PKA catalytic subunit