Game of Frontier Orbitals: A View on the Rational Design of Novel Charge-Transfer Materials

Since the first application of frontier molecular orbitals (FMOs) to rationalize stereospecificity of pericyclic reactions, FMOs have remained at the forefront of chemical theory. Yet, the practical application of FMOs in the rational design and synthesis of novel charge transfer materials remains under-appreciated. In this Perspective, we demonstrate that molecular orbital theory is a powerful and universal tool capable of rationalizing the observed redox/optoelectronic properties of various aromatic hydrocarbons in the context of their application as charge-transfer materials. Importantly, the inspection of FMOs can provide instantaneous insight into the interchromophoric electronic coupling and polaron delocalization in polychromophoric assemblies, and therefore is invaluable for the rational design and synthesis of novel materials with tailored properties

Vertical vs. Adiabatic Ionization Energies in Solution and Gas-Phase: Probing Ionization-Induced Reorganization in Conformationally-Mobile Bichromophoric Actuators Using Photoelectron Spectroscopy, Electrochemistry and Theory

Ionization-induced structural and conformational reorganization in various π-stacked dimers and covalently linked bichromophores is relevant to many processes in biological systems and functional materials. In this work, we examine the role of structural, conformational, and solvent reorganization in a set of conformationally mobile bichromophoric donors, using a combination of gas-phase photoelectron spectroscopy, solution-phase electrochemistry, and density functional theory (DFT) calculations. Photoelectron spectral analysis yields both adiabatic and vertical ionization energies (AIE/VIE), which are compared with measured (adiabatic) solution-phase oxidation potentials (Eox). Importantly, we find a strong correlation of Eox with AIE, but not VIE, reflecting variations in the attendant structural/conformational reorganization upon ionization. A careful comparison of the experimental data with the DFT calculations allowed us to probe the extent of charge stabilization in the gas phase and solution and to parse the reorganizational energy into its various components. This study highlights the importance of a synergistic approach of experiment and theory to study ionization-induced structural and conformational reorganization

Spreading Electron Density Thin: Increasing the Chromophore Size in Polyaromatic Wires Decreases Interchromophoric Electronic Coupling

The development of novel polychromophoric materials using extended polycyclic aromatic hydrocarbons as a single large chromophore holds promise for long-range charge-transfer applications in photovoltaic devices and molecular electronics. However, it is not well-understood how the interchromophoric electronic coupling varies with the chromophore size in linearly connected molecular wires. Here, we show with the aid of electrochemistry, electronic spectroscopy, density functional theory calculations, and theoretical modeling that as the number of aromatic moieties in a single chromophore increases, the interchromophoric electronic coupling decreases and may reach negligible values if the chromophore is sufficiently large. The origin of this initially surprising result becomes clear when one considers this problem with the aid of Hückel molecular orbital theory, as at the polymeric limit energies of the molecular orbitals cluster to form bands and thus the energy spacing between orbitals, and thereby the electronic coupling must decrease with the chromophore expansion

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

Strength of π-Stacking, from Neutral to Cation: Precision Measurement of Binding Energies in an Isolated π-Stacked Dimer

π-Stacking interactions are ubiquitious across chemistry and biochemistry, impacting areas from organic materials and photovoltaics to biochemistry and DNA. However, experimental data is lacking regarding the strength of π-stacking forces—an issue not settled even for the simplest model system, the isolated benzene dimer. Here, we use two-color appearance potential measurements to determine the binding energies of the isolated, π-stacked dimer of fluorene (C13H10) in ground, excited, and ionic states. Our measurements provide the first precise values for π-stacking interaction energies in these states, which are key benchmarks for theory. Indeed, theoretical predictions using ab initio and carefully benchmarked DFT methods are in excellent agreement with experiment

N=4, 3D Supersymmetric Quantum Mechanics in Non-Abelian Monopole Background

Using the harmonic superspace approach, we construct the three-dimensional N=4 supersymmetric quantum mechanics of the supermultiplet (3,4,1) coupled to an external SU(2) gauge field. The off-shell N=4 supersymmetry requires the gauge field to be a static form of the 't Hooft ansatz for the 4D self-dual SU(2) gauge fields, that is a particular solution of Bogomolny equations for BPS monopoles. We present the explicit form of the corresponding superfield and component actions, as well as of the quantum Hamiltonian and N=4 supercharges. The latter can be used to describe a more general N=4 mechanics system, with an arbitrary BPS monopole background and on-shell N=4 supersymmetry. The essential feature of our construction is the use of semi-dynamical spin (4,4,0) multiplet with the Wess-Zumino type action.Comment: 16 pages, reference added, published versio

The Role of Torsional Dynamics on Hole and Exciton Stabilization in π‐Stacked Assemblies: Design of Rigid Torsionomers of a Cofacial Bifluorene

Exciton and charge delocalization across π‐stacked assemblies is of importance in biological systems and functional polymeric materials. To examine the requirements for exciton and hole stabilization, cofacial bifluorene (F2) torsionomers were designed, synthesized, and characterized: unhindered (model) MeF2, sterically hindered tBuF2, and cyclophane‐like CF2, where fluorenes are locked in a perfect sandwich orientation via two methylene linkers. This set of bichromophores with varied torsional rigidity and orbital overlap shows that exciton stabilization requires a perfect sandwich‐like arrangement, as seen by strong excimeric‐like emission only in CF2 and MeF2. In contrast, hole delocalization is less geometrically restrictive and occurs even in sterically hindered tBuF2, as judged by 160 mV hole stabilization and a near‐IR band in the spectrum of its cation radical. These findings underscore the diverse requirements for charge and energy delocalization across π‐stacked assemblies

An Electron‐Rich Calix[4]arene‐Based Receptor with Unprecedented Binding Affinity for Nitric Oxide

Calixarenes have found widespread application as building blocks for the design and synthesis of functional materials in host–guest chemistry. The ongoing desire to develop a detailed understanding of the nature of NO bonding to multichromophoric π‐stacked assemblies led us to develop an electron‐rich methoxy derivative of calix[4]arene (3), which we show exists as a single conformer in solution at ambient temperature. Here, we examine the redox properties of this derivative, generate its cation radical (3+.) using robust chemical oxidants, and determine the relative efficacy of its NO binding in comparison with model calixarenes. We find that 3/3+. is a remarkable receptor for NO+/NO, with unprecedented binding efficacy. The availability of precise experimental structures of this calixarene derivative and its NO complex, obtained by X‐ray crystallography, is critically important both for developing novel functional NO biosensors, and understanding the role of stacked aromatic donors in efficient NO binding, which may have relevance to biological NO transport

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