Singlet fission (SF) has the potential to supersede the traditional solar energy conversion scheme by means of boosting the photonto-current conversion efficiencies beyond the 30% ShockleyQueisser limit. Here, we show unambiguous and compelling evidence for unprecedented intramolecular SF within regioisomeric pentacene dimers in room-temperature solutions, with observed triplet quantum yields reaching as high as 156 ± 5%. Whereas previous studies have shown that the collision of a photoexcited chromophore with a ground-state chromophore can give rise to SF, here we demonstrate that the proximity and sufficient coupling through bond or space in pentacene dimers is enough to induce intramolecular SF where two triplets are generated on one molecule.acene oligomers | excited states | singlet fission | multireference perturbation theory | time-resolved spectroscopy S inglet fission (SF) is a spin-allowed process to convert one singlet excited state into two triplet excited states, namely a correlated triplet pair (1). The ability to effectively implement SF processes in solar cells could allow for more efficient harvesting of high-energy photons from the solar spectrum and allow for the design of solar cells to circumvent the Shockley-Queisser performance limit (2). Indeed, several recent studies have demonstrated remarkably efficient solar cell devices based on SF (3-6).One requirement that needs to be met to achieve SF is that the photoexcited chromophore in its singlet excited state must share its energy with a neighboring ground-state chromophore. As such, the potential of coupled chromophores to afford two triplet excited states via SF has been elucidated in, for example, a tetracene dimer with an SF yield of around 3% (3, 7). Additionally, past experiments in single-crystal, polycrystalline, and amorphous solids of pentacene have documented that the efficiency of SF relates to the electronic coupling between these two chromophores (8, 9). Hence, molecular ordering in terms of crystal packing, that is, proximity, distances, orbital overlap, etc., is decisive with respect to gaining full control over and to finetuning interchromophoric interactions in the solid state (10, 11). Of equal importance are the thermodynamic requirements, namely that the energy of the lowest-lying singlet absorbing state must match or exceed the energy of two triplet excited states (S 1 ≥ 2T 1 ) (11). In light of both aspects, hydrocarbons such as acenes--tetracene, pentacene, hexacene--and their derivatives are at the forefront of investigations toward a sound understanding and development of molecular building blocks for SF. In tetracenes, the singlet-and triplet-pair energy levels are nearly degenerate (S 1 = 2T 1 ), leaving no or little standard enthalpy of reaction for SF (12). In solution, the latter is, however, offset by sizable entropy rendering the process rather slow and, thus, inefficient (13). In addition, the low SF yield relates to the dimer geometry. Its nature hinders electronic coupling through space, leaving only thro...
The components of petroleum asphaltenes exhibit complex bridged structures comprising sulfur, nitrogen, aromatic, and naphthenic groups linked by alkyl chains. These components aggregate in crude oil and toluene over a wide range of concentrations and temperatures, exhibit strong adhesion to a wide range of surfaces, occlude components that are otherwise soluble, are porous to solvents, and are elastic under tension. None of these properties is consistent with an architecture dominated only by aromatic stacking by electrostatic and/or van der Waals forces, often called π–π stacking. We propose an alternate paradigm based on supramolecular assembly of molecules, combining cooperative binding by Brønsted acid–base interactions, hydrogen bonding, metal coordination complexes, and interactions between cylcoalkyl and alkyl groups to form hydrophobic pockets, in addition to aromatic π–π stacking. A range of architectures are suggested, which almost certainly occur simultaneously, including porous networks and host–guest complexes. The latter may include organic clathrates, in which occluded guest molecules stabilize the assembly of a cage, as methane does in gas hydrates. This model has a number of implications for analysis of asphaltene mixtures and predicting asphaltene phase behavior and transport properties.
Carbyne is an allotrope of carbon composed of sp-hybridized carbon atoms. Although its formation in the laboratory is suggested, no well-defined sample is described. Interest in carbyne and its potential properties remains intense because of, at least in part, technological breakthroughs offered by other carbon allotropes, such as fullerenes, carbon nanotubes and graphene. Here, we describe the synthesis of a series of conjugated polyynes as models for carbyne. The longest of the series consists of 44 contiguous acetylenic carbons, and it maintains a framework clearly composed of alternating single and triple bonds. Spectroscopic analyses for these polyynes reveal a distinct trend towards a finite gap between the highest occupied molecular orbital and the lowest unoccupied molecular orbital for carbyne, which is estimated to be ∼485 nm (∼2.56 eV). Even the longest members of this series of polyynes are not particularly sensitive to light, moisture or oxygen, and they can be handled and characterized under normal laboratory conditions.
With the Fritsch-Buttenberg-Wiechell rearrangement as a primary synthetic route, a series of conjugated, triisopropylsilyl end-capped polyynes containing 2-10 acetylene units has been assembled. In a few steps, significant quantities of the polyynes are made available, which allow for a thorough analysis of their structural, physical, and optical properties. Molecules in the series have been characterized in detail using (13)C NMR spectroscopy, differential scanning calorimetry, mass spectrometry, and, for four derivatives including octayne 6, X-ray crystallography. UV-vis spectroscopy of the polyynes 1-7 shows a consistent lowering of the HOMO-LUMO gap (E(g)) as a function of the number of acetylene units (n), fitting a power-law relationship of E(g) approximately n(-)(0.379)(+/-)(0.002). The third-order nonlinear optical (NLO) properties of the polyyne series have been examined, and the nonresonant molecular second hyperpolarizabilities (gamma) increase as a function of length according to the power-law gamma approximately n(4.28)(+/-)(0.13). This result exhibits an exponent that is larger than theoretically predicted for polyynes and higher than is observed for polyenes and polyenynes. The combined linear and nonlinear optical results confirm recent theoretical studies that suggest polyynes as model 1-D conjugated systems. On the basis of UV-vis spectroscopic analysis, the effective conjugation length for this series of polyynes is estimated to be ca. n = 32, providing insight into characteristics of carbyne.
This review provides a discussion of the current state of research on linear carbon structures and related materials based on sp-hybridization of carbon atoms ( polyynes and cumulenes). We show that such systems have widely tunable properties and thus represent an intriguing and mostly unexplored field for both fundamental and applied sciences. We discuss the rich interplay between the structural, vibrational, and electronic properties focusing on recent advances and the future perspectives of carbon-atom wires and novel hybrid sp-sp 2 -carbon architectures.
When molecular dimers, crystalline films or molecular aggregates absorb a photon to produce a singlet exciton, spin-allowed singlet fission may produce two triplet excitons that can be used to generate two electron–hole pairs, leading to a predicted ∼50% enhancement in maximum solar cell performance. The singlet fission mechanism is still not well understood. Here we report on the use of time-resolved optical and electron paramagnetic resonance spectroscopy to probe singlet fission in a pentacene dimer linked by a non-conjugated spacer. We observe the key intermediates in the singlet fission process, including the formation and decay of a quintet state that precedes formation of the pentacene triplet excitons. Using these combined data, we develop a single kinetic model that describes the data over seven temporal orders of magnitude both at room and cryogenic temperatures.
Scientists have sought for over two decades to incorporate the necessary attributes of transparency, stability, and high nonlinear susceptibilities into optimized organic or organometallic chromophores for third-order nonlinear optical (NLO) applications. These investigations have provided an ever-expanding understanding of structure−function relationships for the second hyperpolarizability γ and the bulk third-order nonlinear optical susceptibility χ(3) in organic materials, which are reviewed herein. Contributing to this understanding are the studies of the third-order NLO properties displayed by an array of structurally related organic chromophores based on the conjugated carbon skeletons of hex-3-ene-1,5-diynes (1,2-diethynylethenes, DEEs) and 3,4-diethynylhex-3-ene-1,5-diynes (tetraethynylethenes, TEEs). A comprehensive series of donor (D) and/or acceptor (A) substituted derivatives of DEEs and TEEs has been measured by third-harmonic generation (THG) experiments, and the investigations on these one- and two-dimensionally conjugated chromophores have provided fundamental insight into routes leading to enhanced optical nonlinearities. The molecular characteristics identified to impact the second hyperpolarizability γ include conjugation length, heteroaromatic conjugation, degree of D/A substitution, cis, trans, and geminal D/A conjugation, and molecular asymmetry. A comparison of NLO properties for small molecular systems to those of a number of larger oligomers based on the DEE and TEE framework is also presented.
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