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ConspectusNature has established a sustainable way to maintain aerobic life on earth by inventing one of the most sophisticated biological processes, namely, natural photosynthesis, which delivers us with organic matter and molecular oxygen derived from the two abundant resources sunlight and water. The thermodynamically demanding photosynthetic water splitting is catalyzed by the oxygen-evolving complex in photosystem II (OEC-PSII), which comprises a distorted tetramanganese-calcium cluster (CaMn4O5) as catalytic core. As an ubiquitous concept for fine-tuning and regulating the reactivity of the active site of metalloenzymes, the surrounding protein domain creates a sophisticated environment that promotes substrate preorganization through secondary, noncovalent interactions such as hydrogen bonding or electrostatic interactions. Based on the high-resolution X-ray structure of PSII, several water channels were identified near the active site, which are filled with extensive hydrogen-bonding networks of preorganized water molecules, connecting the OEC with the protein surface. As an integral part of the outer coordination sphere of natural metalloenzymes, these channels control the substrate and product delivery, carefully regulate the proton flow by promoting pivotal proton-coupled electron transfer processes, and simultaneously stabilize short-lived oxidized intermediates, thus highlighting the importance of an ordered water network for the remarkable efficiency of the natural OEC.Transferring this concept from nature to the engineering of artificial metal catalysts for fuel production has fostered the fascinating field of metallosupramolecular chemistry by generating defined cavities that conceptually mimic enzymatic pockets. However, the application of supramolecular approaches to generate artificial water oxidation catalysts remained scarce prior to our initial reports, since such molecular design strategies for efficient activation of substrate water molecules in confined nanoenvironments were lacking. In this Account, we describe our research efforts on combining the state-of-the art Ru(bda) catalytic framework with structurally programmed ditopic ligands to guide the water oxidation process in defined metallosupramolecular assemblies in spatial proximity. We will elucidate the governing factors that control the quality of hydrogen-bonding water networks in multinuclear cavities of varying sizes and geometries to obtain high-performance, state-of-the-art water oxidation catalysts. Pushing the boundaries of artificial catalyst design, embedding a single catalytic Ru center into a well-defined molecular pocket enabled sophisticated water preorganization in front of the active site through an encoded basic recognition site, resulting in high catalytic rates comparable to those of the natural counterpart OEC-PSII.To fully explore their potential for solar fuel devices, the suitability of our metallosupramolecular assemblies was demonstrated under (electro)chemical and photocatalytic water oxidation conditions. In addition, testing the limits of structural diversity allowed the fabrication of self-assembled linear coordination oligomers as novel photocatalytic materials and long-range ordered covalent organic framework (COF) materials as recyclable and long-term stable solid-state materials for future applications.
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The reversible condensation of catechols and boronic acids to boronate esters is a paradigm reaction in dynamic covalent chemistry. However, facile backward hydrolysis is detrimental for stability and has so far prevented applications for boronate-based materials. Here, we introduce cubic boronate ester cages 6 derived from hexahydroxy tribenzotriquinacenes and phenylene diboronic acids with ortho-t-butyl substituents. Due to steric shielding, dynamic exchange at the Lewis acidic boron sites is feasible only under acid or base catalysis but fully prevented at neutral conditions. For the first time, boronate ester cages 6 tolerate substantial amounts of water or alcohols both in solution and solid state. The unprecedented applicability of these materials under ambient and aqueous conditions is showcased by efficient encapsulation and on-demand release of ß-carotene dyes and heterogeneous water oxidation catalysis after the encapsulation of ruthenium catalysts.
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The encapsulation of more than one guest molecule into a synthetic cavity is a highly desirable yet a highly challenging task to achieve for neutral supramolecular hosts in organic media. Herein, we report a neutral perylene bisimide cyclophane, which has a tailored chiral cavity with an interchromophoric distance of 11.2 Å, capable of binding two aromatic guests in a π-stacked fashion. Detailed host-guest binding studies with a series of aromatic guests revealed that the encapsulation of the second guest in this cyclophane is notably more favored than the first one. Accordingly, for the encapsulation of the coronene dimer, a cooperativity factor (α) as high as 485 was observed, which is remarkably high for neutral host-guest systems. Furthermore, a successful chirality transfer, from the chiral host to encapsulated coronenes, resulted in a chiral charge-transfer (CT) complex and the rare observation of circularly polarized emission originating from the CT state for a noncovalent donor-acceptor assembly in solution. The involvement of the CT state also afforded an enhancement in the luminescence dissymmetry factor (glum) value due to its relatively large magnetic transition dipole moment. The 1:2 binding pattern and chirality-transfer were unambiguously verified by single-crystal X-ray diffraction analysis of the host-guest superstructures.
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Activating delayed fluorescence emission in a dilute solution via a non-covalent approach is a formidable challenge. In this report, we propose a strategy for efficient delayed fluorescence generation in dilute solution using a non-covalent approach via supramolecularly engineered cyclophane-based nanoenvironments that provide sufficient binding strength to π-conjugated guests and that can stabilize triplet excitons by reducing vibrational dissipation and lowering the singlet-triplet energy gap for efficient delayed fluorescence emission. Toward this goal, a novel biphenyl bisimide-derived cyclophane is introduced as an electron-deficient and efficient triplet-generating host. Upon encapsulation of various carbazole-derived guests inside the nanocavity of this cyclophane, emissive charge transfer (CT) states close to the triplet energy level of the biphenyl bisimide are generated. The experimental results of host-guest studies manifest high association constants up to 104 M-1 as the prerequisite for inclusion complex formation, the generation of emissive CT states, and triplet-state stabilization in a diluted solution state. By means of different carbazole guest molecules, we could realize tunable delayed fluorescence emission in this carbazole-encapsulated biphenyl bisimide cyclophane in methylcyclohexane/carbon tetrachloride solutions with a quantum yield (QY) of up to 15.6%. Crystal structure analyses and solid-state photophysical studies validate the conclusions from our solution studies and provide insights into the delayed fluorescence emission mechanism.
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Dissymmetrical chiral peropyrenes with electron-rich and electron-deficient aryl substituents in the bay regions were synthesized via iridium-catalyzed C-H activation and alkyne benzannulation. The electronic properties were studied using cyclic and differential pulse voltammetry. The enantiomers were separated and exhibited high glum and gabs values in circularly polarized luminescence (CPL) and circular dichroism (CD), respectively. Variable-temperature NMR experiments were conducted on symmetrical and dissymmetrical chiral peropyrenes to compare the barrier to rotation of the aryl groups in the bay region.
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Charged molecules play essential roles in many natural and artificial functional processes, ranging from photosynthesis to photovoltaics to chemical reactions and more. It is often difficult to identify the optical dynamic properties of relevant redox species because they cannot be easily prepared, their spectra overlap, or they evolve on a femtosecond timescale. Here, we address these challenges by combining spectroelectrochemistry, ultrafast transient absorption spectroscopy, and suitable data analysis. We illustrate the method with the various redox species of a cyclophane composed of two perylene bisimide subunits. While singular-value decomposition is a well-established tool in the analysis of time-dependent spectra of a single molecular species, we here use it additionally to separate transient maps of individual redox species. This is relevant because at any specific applied electrochemical potential, several redox species coexist in the ensemble, and our procedure allows disentangling their spectroscopic response. In the second step, global analysis is then employed to retrieve the excited-state lifetimes and decay-associated difference spectra. Our approach is generally suitable for unraveling ultrafast dynamics in materials featuring charge-transfer processes.
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Near-Infrared (NIR) phosphorescence at room temperature is challenging to achieve for organic molecules due to negligible spin-orbit coupling and a low energy gap leading to fast non-radiative transitions. Here, we show a supramolecular host-guest strategy to harvest the energy from the low-lying triplet state of C64 nanographene tetraimide 1. 1Hâ NMR and X-ray analysis confirmed the 1 : 2 stoichiometric binding of a Pt(II) porphyrin on the two π-surfaces of 1. While the free 1 does not show emission in the NIR, the host-guest complex solution shows NIR phosphorescence at 77â K. Further, between 860-1100â nm, room temperature NIR phosphorescence (λmax=900â nm, τavg=142â µs) was observed for a solid-state sample drop-casted from a preformed complex in solution. Theoretical calculations reveal a non-zero spin-orbit coupling between isoenergetic S1 and T3 of π-stacked [1 â Pt(II) porphyrin] complex. External heavy-atom-induced spin-orbit coupling along with rigidification and protection from oxygen in the solid-state promotes both the intersystem crossing from the first excited singlet state into the triplet manifold and the NIR phosphorescence from the lowest triplet state of 1.
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Harvesting triplet excitons of heavy atom-free purely organic chromophores under aerated conditions is challenging due to the quenching of long-lived triplet states by molecular oxygen and vibrational dissipation. Herein, we show a supramolecular approach of triplet harvesting via mitigating quenching pathways of a triplet harvester. Specifically, we used a host-guest system based on 2,3:6,7ânaphthalene bis(dicarboximide)-derived cyclophane (NBICy) and carbazole derivative (EtCz). Complexation studies and single-crystal X-ray analysis showed the formation of a rigid host-guest complex (K = ~104 M-1 in CCl4), resulting in triplet-exciton stabilization under aerated conditions via mitigating vibrational interference and oxygen quenching. Photophysical studies elucidate the delayed fluorescence emission from the charge-transfer state (1CT) with a quantum yield (QY) of 6-8% under ambient conditions which increased up to 36 % in an inert atmosphere.
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The dynamic nature of calamitic liquid crystals is exploited to perform isothermal phase transitions driven by dynamic covalent chemistry. For this purpose, nematic (N) arrays based on aldehyde 1 were treated with different amines (A-E) in an on-surface process, which resulted in different isothermal phase transitions. These phase transformations were caused by in situ imination reactions and are dependent on the nature of the added amine. Transitions from the N to crystal (1A, 1E), isotropic (1B), and smectic (Sm) (1C, 1D) phases were achieved, while the resulting materials feature thermotropic liquid crystal behavior. A sequential transformation from the N 1 to the Sm 1C and then to the N 1B was achieved by coupling an imination to a transimination processes and adjusting the temperature. All of these processes were well characterized by microscopic, spectroscopic, and X-ray techniques, unlocking not only the constitutional but also the structural aspects of the phase transitions. This work provides new insights into designing constitutionally and structurally adaptable liquid crystal systems, paving the way toward the conception of programable evolutive pathways and adaptive materials.
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π-π interactions are among the most important intermolecular interactions in supramolecular systems. Here we determine experimentally a universal parameter for their strength that is simply based on the size of the interacting contact surfaces. Toward this goal we designed a new cyclophane based on terrylene bisimide (TBI) π-walls connected by para-xylylene spacer units. With its extended π-surface this cyclophane proved to be an excellent and universal host for the complexation of π-conjugated guests, including small and large polycyclic aromatic hydrocarbons (PAHs) as well as dye molecules. The observed binding constants range up to 108â M-1 and show a linear dependence on the 2D area size of the guest molecules. This correlation can be used for the prediction of binding constants and for the design of new host-guest systems based on the herewith derived universal Gibbs interaction energy parameter of 0.31â kJ/molÅ2 in chloroform.
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Replacement of sp2-hybridized carbon in polycyclic aromatic hydrocarbons (PAHs) by boron affords electron-deficient π-scaffolds due to the vacant pz-orbital of three-coordinate boron with the potential for pronounced electronic interactions with electron-rich metal surfaces. Using a diboraperylene diborinic acid derivative as precursor and a controlled on-surface non-covalent synthesis approach, we report on a self-assembled chiral supramolecular kagome network on an Ag(111) surface stabilized by intermolecular hydrogen-bonding interactions at low temperature. Scanning tunneling microscopy (STM) and spectroscopy (STS) reveal a flat band at ca. 0.33â eV above the Fermi level which is localized at the molecule center, in good agreement with tight-binding model calculations of flat bands characteristic for kagome lattices.
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Two [n]heliceno-bis(naphthalimides) 1 and 2 (n = 5 and 6, respectively) where two electron-accepting naphthalimide moieties are attached at both ends of helicene core were synthesized by effective two-step strategy, and their enantiomers could be resolved by chiral stationary-phase high-performance liquid chromatography (HPLC). The single-crystal X-ray diffraction analysis of enantiopure fractions of 1 and 2 confirmed their helical structure, and together with experimental and calculated circular dichroism (CD) spectra, the absolute configuration was unambiguously assigned. Both 1 and 2 exhibit high molar extinction coefficients for the S0-S1 transition and high fluorescence quantum yields (73% for 1 and 69% for 2), both being outstanding for helicene derivatives. The red circularly polarized luminescence (CPL) emission up to 615 nm for 2 with CPL brightness (BCPL) up to 66.5 M-1 cm-1 demonstrates its potential for applications in chiral optoelectronics. Time-dependent density functional theory (TD-DFT) calculations unambiguously showed that the large transition magnetic dipole moment |m| of 2 is responsible for its high absorbance dissymmetry (gabs) and luminescence dissymmetry (glum) factor.
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Chiral polycyclic aromatic hydrocarbons can be tailored for next-generation photonic materials by carefully designing their molecular as well as supramolecular architectures. Hence, excitonic coupling can boost the chiroptical response in extended aggregates but is still challenging to achieve by pure self-assembly. Whereas most reports on these potential materials cover the UV and visible spectral range, systems in the near infrared (NIR) are underdeveloped. We report a new quaterrylene bisimide derivative with a conformationally stable twisted π-backbone enabled by the sterical congestion of a fourfold bay-arylation. Rendering the π-subplanes accessible by small imide substituents allows for a slip-stacked chiral arrangement by kinetic self-assembly in low polarity solvents. The well dispersed solid-state aggregate reveals a sharp optical signature of strong J-type excitonic coupling in both absorption (897 nm) and emission (912 nm) far in the NIR region and reaches absorption dissymmetry factors up to 1.1 × 10-2. The structural elucidation was achieved by atomic force microscopy and single-crystal X-ray analysis which we combined to derive a structural model of a fourfold stranded enantiopure superhelix. We could deduce that the role of phenyl substituents is not only granting stable axial chirality but also guiding the chromophore into a chiral supramolecular arrangement needed for strong excitonic chirality.
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Molecular chaperones are proteins that assist in the (un)folding and (dis)assembly of other macromolecular structures toward their biologically functional state in a non-covalent manner. Transferring this concept from nature to artificial self-assembly processes, here, we show a new strategy to control supramolecular polymerization via a chaperone-like two-component system. A new kinetic trapping method was developed that enables efficient retardation of the spontaneous self-assembly of a squaraine dye monomer. The suppression of supramolecular polymerization could be regulated with a cofactor, which precisely initiates self-assembly. The presented system was investigated and characterized by ultraviolet-visible, Fourier transform infrared, and nuclear magnetic resonance spectroscopy, atomic force microscopy, isothermal titration calorimetry, and single-crystal X-ray diffraction. With these results, living supramolecular polymerization and block copolymer fabrication could be realized, demonstrating a new possibility for effective control over supramolecular polymerization processes.
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Mathematical models for the concentration-, temperature- and solvent-dependent analysis of self-assembly equilibria are derived for the most simple case of dimer formation, to highlight the assumptions these models and the thus determined thermodynamic parameters are based on. The three models were applied to UV/Vis absorption data for the dimerization of a highly dipolar merocyanine dye in 1,4-dioxane. Isothermal titration calorimetry (ITC) dilution experiments were performed as an independent reference technique. While the concentration-dependent analysis is according to our studies the most reliable method, also the less time-consuming temperature-dependent evaluation can give accurate results in the present example, despite small thermochromic effects. In contrast, the strong negative solvatochromism of the merocyanine tampers with the results from the solvent-dependent evaluation. Even though the studies presented in this work are limited to the monomer-dimer equilibrium of a dipolar dye, the basic principles can be transferred to other chromophores and different self-assembly models, including those for supramolecular polymerization.
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Five chiral squaraine dimers were synthesized by fusing chiral indolenine semisquaraines with three different benzobisthiazole bridges. The thereby created squaraine dimers show a strong splitting of the lowest energy absorption bands caused by exciton coupling. The intensities of the two exciton transitions and the energetic splitting depend on the angle of the two squaraine moieties within the chromophore dimer. The electric circular dichroism spectra of the dimers show intense Cotton effects whose sign depends on the used squaraine chromophores. Sizable anisotropies gabs of up to 2.6 × 10-3 could be obtained. TD-DFT calculations were used to partition the rotational strength into the three Rosenfeld terms where the electric-magnetic coupling turned out to be the dominant contribution while the exciton chirality term is much smaller. This is because the chromophore dimers are essentially planar but the angle between the electric transition dipole moment of one squaraine and the magnetic transition dipole moment of the other squaraine strongly deviates from 90°, which makes the dot product between the two moment vectors and, thus, the rotational strength substantial.
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Perylene bisimides are widely studied due to their various applications. Most research is carried out on neutral molecules but charged species are essential in the context of organic electronics and photovoltaics. In this study, we carry out ultrafast transient absorption spectroelectrochemistry and coherent two-dimensional electronic spectroelectrochemistry on three different neutral perylene bisimide derivatives as well as their singly and doubly reduced species. We compare an unsubstituted, flat parent perylene bisimide with two twisted ones that introduce spin-orbit coupling, leading to enhanced intersystem crossing. The internal conversion from higher excited states to the lowest electronically excited state occurs in the picosecond regime with lifetimes significantly shorter for the charged species compared to the neutral ones. Coherent oscillations of the transients for the flat dianion of parent perylene bisimide indicate the occurrence of Fermi resonance. The corresponding vibrational coupling and the superposition of the participating vibrational modes may lead to an enhanced charge separation and triplet formation.
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The efficient population of the triplet excited states in heavy metal-free organic chromophores has been one of the long-standing research problems to molecular photochemists. The negligible spin-orbit coupling matrix elements in the purely organic chromophores and the large singlet-triplet energy gap (ΔES-T) pose a hurdle for ultrafast intersystem crossing (ISC). Herein we report the unprecedented population of triplet manifold in a series of nitrogen-annulated perylene bisimide chromophores (NPBI and Br-NPBI). NPBI is found to have a moderate fluorescence quantum yield (Φf = 68 ± 5%), whereas Br-NPBI showcased a low fluorescence quantum yield (Φf = 2.0 ± 0.6%) in toluene. The femtosecond transient absorption measurements of Br-NPBI revealed ultrafast ISC (kISC = 1.97 × 1010 s-1) from the initially populated singlet excited state to the long-lived triplet excited states. The triplet quantum yields (ΦT = 95.2 ± 4.6% for Br-NPBI, ΦT = 18.7 ± 2.3% for NPBI) calculated from nanosecond transient absorption spectroscopy measurements showed the enhancement in triplet population upon bromine substitution. The quantum chemical calculations revealed the explicit role of nitrogen annulation in tuning the excited state energy levels to favor the ISC. The near degeneracy between the singlet and triplet excited states observed in NPBI and Br-NPBI (ΔES-T = -0.01 eV for NPBI, ΔES-T = 0.03 eV for Br-NPBI) facilitates the spin flipping in the molecules. Nitrogen annulation emerges as a design strategy to open up the ISC pathway and the rate of which can be further enhanced by the substitution of a heavier element.
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Phthalocyanines are extensively used by the dye and pigment industry and in photovoltaic and photodynamic therapy research due to their intense absorption of visible light, outstanding stability, and versatility. As pigments, the unsubstituted phthalocyanines are insoluble owing to strong intermolecular π-π-stacking interactions, which causes limitations for the solution chemistry for both free base and metalated phthalocyanines. Here we show a supramolecular host-guest strategy to dissolve phthalocyanines into solution. C64 nanographene tetraimide (1) binds two free base/zinc/copper phthalocyanines in a 1 : 2 stoichiometry to solubilize phthalocyanines as evidenced by 1 Hâ NMR spectroscopy, UV/Vis absorption and single-crystal X-ray analysis. Binding studies using a tetra-tert-butyl-substituted soluble phthalocyanine revealed binding affinities of up to 109 â M-1 in tetrachloromethane, relating to a Gibbs free energy of -52â kJ mol-1 . Energy decomposition analysis revealed that complexes between 1 and phthalocyanines are stabilized by dispersion interactions followed by electrostatics as well as significant charge-transfer interactions.
Assuntos
Isoindóis , Fotoquimioterapia , Fenômenos Químicos , LuzRESUMO
Proton-coupled electron-transfer (PCET) processes play a key role in biocatalytic energy conversion and storage, for example, photosynthesis or nitrogen fixation. Here, we report a series of bipyridine-containing di- to tetranuclear Ru(bda) macrocycles 2 C-4 C (bda: 2,2'-bipyridine-6,6'-dicarboxylate) to promote O-O bond formation. In photocatalytic water oxidation under neutral conditions, all complexes 2 C-4 C prevail in a folded conformation that support the water nucleophilic attack (WNA) pathway with remarkable turnover frequencies of up to 15.5â s-1 per Ru unit respectively. Single-crystal X-ray analysis revealed an increased tendency for intramolecular π-π stacking and preorganization of the proximal bases close to the active centers for the larger macrocycles. H/D kinetic isotope effect studies and electrochemical data demonstrate the key role of the proximal bipyridines as proton acceptors in lowering the activation barrier for the crucial nucleophilic attack of H2 O in the WNA mechanism.