Search

Excimers usually serve as low energy trap sites in supramolecular chromophore assemblies; however, if the trap is not too deep, excimers may diffuse throughout the structure, making it possible to ...

Covalent chromophore dimers having the required energetics can undergo intramolecular singlet fission (SF) in solution; however, in the solid state, intra- and intermolecular SF can compete. Here, ...

The phenomenon of photon upconversion, in which a system absorbs two or more photons of lower energy and emits a photon of higher energy, has been used in numerous applications, including non-destructive bioimaging, deep-penetrating photodynamic therapy, catalysis, and photovoltaic devices. To date, photon upconversion has been observed typically in inorganic nanocrystals, nanoparticles, metal-organic frameworks, supramolecular assemblies, and organic dyads. Herein, we demonstrate a new strategy for harnessing photon upconversion-supramolecular upconversion-based on host-guest chemistry. We have identified a box-like fluorescent tetracationic host incorporating a thiazolothiazole emitter, which can accommodate a guest-sensitizer, 5,15-diphenylporphyrin, inside its cavity, and demonstrated that the host-guest inclusion complex displays triplet-fusion upconversion when the guest is excited with low-energy light. The strategy of supramolecular upconversion has been employed successfully in two other host-guest complexes-with hosts comprised of anthracene emitters and a 5,15-diphenylporphyrin guest-corroborating the fact that this strategy is a general one and can be applied to the design of a new family of host-guest complexes for photon upconversion. More importantly, supramolecular upconversion is accessible in solution under dilute conditions (μM) compared to most of the existing approaches that require significantly higher concentrations (mM) of emitters and/or sensitizers. Transient absorption spectroscopy and density functional theory have been employed in order to confirm a triplet-fusion upconversion mechanism. Host-guest complexation-mediated supramolecular photon upconversion eliminates multiple issues in the existing systems related to high working concentrations, high incident laser power, and low optical penetration depths.

Switchable coupling between two qubits is important for quantum information science (QIS). As a proof of concept, a series of mesosubstituted porphyrins have been synthesized with a (2,2,6,6-tetramethylpiperidin-1-yl)oxyl stable free radical (SFR) appended and metalated with Cu(II), Ni(II), and Zn(II) in order to explore the interaction between the SFR doublet state and metalloporphyrin. The spin state of the porphyrin varies upon metal insertion, where Zn(II) is a diamagnetic metal, Cu(II) is paramagnetic, and Ni(II) can be switched from a diamagnetic square-planar structure to a paramagnetic octahedral state by complexation with a solvent (i.e., pyridine or tetrahydrofuran). Time-resolved electron paramagnetic resonance (EPR) measurements reveal that upon photoexcitation, the Zn(II) and free-base porphyrin species demonstrate different magnetic exchange regimes between the porphyrin triplet excited states and the SFR doublet state, with the Zn derivative populating a quartet state (i.e., moderate magnetic exchange), whereas the free-base derivative remains a triplet (i.e., weak magnetic exchange). Transient absorption measurements corroborate the TREPR results, demonstrating a 66% increase in the singlet excited-state decay rate due to enhanced intersystem crossing for the Zn(II) derivative in comparison to a modest 14% enhancement for the free-base porphyrin. These results enable the realization of a switchable qubit coupler, depending upon Zn metal insertion to the free-base porphyrin, which has potential QIS applications.

We report how the nanoconfined environment, introduced by the mechanical bonds within an electrochemically switchable bistable [2]rotaxane, controls the rotation of a fluorescent molecular rotor, namely an 8-phenyl-substituted boron dipyrromethene (BODIPY). The electrochemical switching of the bistable [2]rotaxane induces changes in the ground-state co-conformation and in the corresponding excited-state properties of the BODIPY rotor. In the starting redox state, when no external potential is applied, the cyclobis(paraquat-p-phenylene) (CBPQT⁴⁺) ring component encircles the tetrathiafulvalene (TTF) unit on the dumbbell component, leaving the BODIPY rotor unhindered and exhibiting low fluorescence. Upon oxidation of the TTF unit to a TTF²⁺ dication the CBPQT⁴⁺ ring is forced toward the molecular rotor leading to an increased energy barrier for the excited-state to rotate the rotor into the state with the high non-radiative rate constant, resulting in an overall 3.4-fold fluorescent enhancement. On the other hand, when the solvent polarity is high enough to stabilize the excited charge transfer state between the BODIPY rotor and the CBPQT⁴⁺ ring, the movement of the ring towards the BODIPY rotor produces an unexpectedly strong fluorescent signal decrease as the result of the photoinduced electron transfer from the BODIPY rotor to the CBPQT⁴⁺ ring. The nanoconfinement effect introduced by mechanical bonding can effectively lead to the modulation of the physicochemical properties as observed in this bistable [2]rotaxane. On account of the straightforward synthetic strategy and the facile modulation of switchable electrochromic behavior, our approach could pave the way for the development of new stimuli-responsive materials based on mechanically interlocked molecules for future electro-optical applications, such as sensors, molecular memories and molecular logic gates.

Chromophore aggregation strongly impacts the efficiency of organic photovoltaics (OPVs). Perylene-3,4:9,10-bis(dicarboximide) (PDI)-based electron acceptors have been shown to be excellent alternat...

Singlet fission (SF) creates two triplet excitons following absorption of a photon by two electronically interacting chromophores. Quaterrylene-3,4:13,14-bis(dicarboximide) (QDI) is a strongly absorbing chromophore that readily fulfills the energetic requirements for SF, E(S1) > 2E(T1), and thus should undergo rapid and efficient SF. SF was studied in thin films of the QDI derivative N,N-bis(2,6-diisopropylphenyl)-QDI (ArQDI), which undergoes SF in

Summary A series of readily accessible and scalable benzo[1,2-b:4,5-b′]dithiophene (BDT)-2,5-dithienyl-thieno[3,4-c]pyrrole-4,6-dione (TPD-T2)-based donor polymers are utilized in organic photovoltaic (OPV) cells blended with the non-fullerene acceptor IT-4F. All polymers readily dissolve in chlorine-free solvents such as xylene, and the corresponding photoactive blend films can be processed in ambient from this solvent to fabricate cells with power conversion efficiencies (PCEs) >12%–14%. Furthermore, the blend processing and OPV metrics are remarkably insensitive to the processing methodology (spin coating versus blade coating), processing solvent, polymer molecular mass and dispersity index, and the results were rationalized by UV-vis, PL, fsTA, AFM, TEM, GIWAXS, and SCLC measurements. These properties enable the first OPV modules, processed in ambient from a benign solvent, with a certified PCE of 10.1% for an area of 20.4 cm2 and >7% after light soaking. The same module also delivers a power of ∼40 μW/cm2 (PCE ∼22%) under indoor lighting.

Organic photovoltaics incorporating non-fullerene acceptors based on perylenediimide (PDI) now rival fullerene acceptor-based devices in performance, although the mechanisms of charge generation in PDI-based devices are not yet fully understood. Fullerene-based systems are proposed to undergo electron transfer directly from the photoexcited donor into a band of delocalized acceptor states, thus increasing charge generation efficiency. Similarly, anion delocalization has been shown to enhance the rate of electron transfer from a photoexcited donor to two electronically coupled PDI acceptors. Here we investigate how additional electron acceptors may further increase the rate of electron transfer from the donor zinc meso-tetraphenylporphyrin (ZnTPP) to an aggregate of PDI acceptors (PDI[Formula: see text]. Femtosecond transient visible and mid-infrared absorption spectroscopies show that the rate of electron transfer from 1*ZnTPP to the PDI assembly ZnTPP2-PDI3 is statistically identical to that of the previously examined ZnTPP-PDI2. A Marcus theory analysis indicates that the parameters governing electron transfer are nearly identical for the two molecules, suggesting that the maximum electron transfer rate enhancement has been achieved in a cofacial PDI dimer because the ZnTPP directly couples to the first two PDI acceptors whereas the coupling to the third PDI is too weak.

Oncogenic mutations within the RAS pathway are common in multiple myeloma (MM), an incurable malignancy of plasma cells. However, the mechanisms of pathogenic RAS signaling in this disease remain enigmatic and difficult to inhibit therapeutically. We employed an unbiased proteogenomic approach to dissect RAS signaling in MM by combining genome-wide CRISPR-Cas9 screening with quantitative mass spectrometry focused on RAS biology. We discovered that mutant isoforms of RAS organized a signaling complex with the amino acid transporter, SLC3A2, and MTOR on endolysosomes, which directly activated mTORC1 by co-opting amino acid sensing pathways. MM tumors with high expression of mTORC1-dependent genes were more aggressive and enriched in RAS mutations, and we detected interactions between RAS and MTOR in MM patient tumors harboring mutant RAS isoforms. Inhibition of RAS-dependent mTORC1 activity synergized with MEK and ERK inhibitors to quench pathogenic RAS signaling in MM cells. This study redefines the RAS pathway in MM and provides a mechanistic and rational basis to target this novel mode of RAS signaling.

The use of Bruton tyrosine kinase (BTK) inhibitors to block B-cell receptor (BCR)–dependent NF-κB activation in lymphoid malignancies has been a major clinical advance, yet acquired therapeutic resistance is a recurring problem. We modeled the development of resistance to the BTK inhibitor ibrutinib in the activated B-cell (ABC) subtype of diffuse large B-cell lymphoma, which relies on chronic active BCR signaling for survival. The primary mode of resistance was epigenetic, driven in part by the transcription factor TCF4. The resultant phenotypic shift altered BCR signaling such that the GTPase RAC2 substituted for BTK in the activation of phospholipase Cγ2, thereby sustaining NF-κB activity. The interaction of RAC2 with phospholipase Cγ2 was also increased in chronic lymphocytic leukemia cells from patients with persistent or progressive disease on BTK inhibitor treatment. We identified clinically available drugs that can treat epigenetic ibrutinib resistance, suggesting combination therapeutic strategies. Significance: In diffuse large B-cell lymphoma, we show that primary resistance to BTK inhibitors is due to epigenetic rather than genetic changes that circumvent the BTK blockade. We also observed this resistance mechanism in chronic lymphocytic leukemia, suggesting that epigenetic alterations may contribute more to BTK inhibitor resistance than currently thought. See related commentary by Pasqualucci, p. 555. This article is highlighted in the In This Issue feature, p. 549

Perylenediimides (PDIs) are important molecular building blocks that are being investigated for their applicability in optoelectronic technologies. Covalently linking multiple PDI acceptors at the 2,5,8,11 (headland) positions adjacent to the PDI carbonyl groups is reported to yield higher power conversion efficiencies in photovoltaic cells relative to PDI acceptors linked at the 1,6,7,12 (bay) positions. While the photophysical properties of PDIs linked via the bay positions have been investigated extensively, those linked at the headland positions have received far less attention. We showed previously that symmetry-breaking charge separation (SB-CS) in PDIs hold promise as a strategy for increasing photovoltaic efficiency. Here we use transient absorption and emission spectroscopies to investigate the competition between SB-CS, fluorescence, and internal conversion in three related PDI dimers linked at the headland positions with o-, m-, and p-phenylene moieties: o-PDI2, m-PDI2, and p-PDI2, respectively. It is found that o-PDI2 supports SB-CS yielding PDI•+-PDI•-, which is in equilibrium with the o-PDI2 first excited state in a polar solvent (CH2Cl2) while m-PDI2 and p-PDI2 exhibit accelerated internal conversion due to the motion of the linker along with subnanosecond intersystem crossing (ISC). Electronic coupling and structural dynamics are shown to play a significant role, with o-PDI2 being the only member of the series that exhibits significant through-bond interchromophore coupling. The pronounced o-PDI2 steric congestion prevents the free internal rotation that leads to rapid deactivation of the excited state in the other dimers.

Guanine-quadruplex (G-quadruplex) assemblies provide a useful platform for studying the spatial, structural, and photophysical effects of intermolecular interactions. Coupling a single guanine moiety to terrylenediimide (TDI)—a chromophore with a large extended π-surface—produces a structure (GTDI) that assembles in plate-like tetramers, with the potential of undergoing tunable π-stacking. At high concentrations (3 × 10–3 M), GTDI self-assembles into a nearly monodisperse G-quadruplex structure of 16 layers, with strong π-overlap between TDI moieties, observed by small- and wide-angle X-ray scattering. Transient absorption spectroscopy reveals that excitation of TDI in the G-quadruplex results in symmetry-breaking charge separation to form ion pairs within the structure, owing to the strong π-overlap enforced by the hydrogen-bonding. These assemblies yield important insights into the interplay of noncovalent interactions in the assembly of ordered chromophoric arrays.

A series of donor-acceptor (D-A) naphthalene-viologen-based cyclophanes of different shapes, sizes, and symmetries have been synthesized and characterized. Solution optical studies on these cyclophanes reveal the existence of photoinduced intramolecular charge transfer (CT) at 465 nm from naphthalene (D) to viologen (A) units, resulting in a conformational change in the viologen units and the emergence of an emission at 540 nm. The D-A cyclophanes with box-like and hexagon-like shapes offer an opportunity to control the arrangement within 2D layers where D-A interactions direct the superstructures. While a box-like 2,6-disubstituted naphthalene-based tetracationic cyclophane does not form square tiling patterns, a truncated hexagon-like congener self-assembles to form a hexagonal superstructure which, in turn, adopts a hexagonal tiling pattern. Tessellation of the more rigid and highly symmetrical 2,7-disubstituted naphthalene-based cyclophanes leads to the formation of 2D square and honeycomb tiling patterns with the box-like and hexagon-like cyclophanes, respectively. Co-crystallization of the box-like cyclophanes with tetrathiafulvalene (TTF) results in the formation of D-A CT interactions between TTF and viologen units, leading to tubular superstructures. Co-crystallization of the hexagon-like cyclophane with TTF generates well-ordered and uniform tubular superstructures in which the TTF-viologen CT interactions and naphthalene-naphthalene [π···π] interactions propagate with 2D topology. In the solid state, the TTF-cyclophane co-crystals are paramagnetic and display dual intra- and intermolecular CT behavior at ∼470 and ∼1000 nm, respectively, offering multi-responsive materials with potential pathways for electron transport.

Quantum teleportation transfers the quantum state of a system over an arbitrary distance from one location to another through the agency of quantum entanglement. Because quantum teleportation is essential to many aspects of quantum information science, it is important to establish this phenomenon in molecular systems whose structures and properties can be tailored by synthesis. Here, we demonstrate electron spin state teleportation in an ensemble of covalent organic donor–acceptor–stable radical (D–A–R•) molecules. Following preparation of a specific electron spin state on R• in a magnetic field using a microwave pulse, photoexcitation of A results in the formation of an entangled electron spin pair D•+–A•−. The spontaneous ultrafast chemical reaction D•+–A•−–R• → D•+–A–R− constitutes the Bell state measurement step necessary to carry out spin state teleportation. Quantum state tomography of the R• and D•+ spin states using pulse electron paramagnetic resonance spectroscopy shows that the spin state of R• is teleported to D•+ with high fidelity. Quantum teleportation moves the quantum state of a system between physical locations without losing its coherence, an essential criterion for emerging quantum information applications. Now, electron-spin-state teleportation in covalent organic electron donor–acceptor–stable radical molecules is demonstrated using entangled electron spins produced by photo-induced electron transfer.

Achieving efficient polymer solar cells (PSCs) requires a structurally optimal donor-acceptor heterojunction morphology. Here we report the combined experimental and theoretical characterization of a benzodithiophene-benzothiadiazole donor polymer series (PBTZF4-R; R = alkyl substituent) blended with the non-fullerene acceptor ITIC-Th, and analyse the effects of substituent dimensions on blend morphology, charge transport, carrier dynamics, and PSC metrics. Varying substituent dimensions has a pronounced effect on the blend morphology with a direct link between domain purity, to some extent domain dimensions, and charge generation and collection. The polymer with the smallest alkyl substituent yields the highest PSC power conversion efficiency (PCE, 11%), reflecting relatively small, high-purity domains, and possibly benefiting from “matched” donor polymer - small molecule acceptor orientations. The distinctive morphologies arising from the substituents are investigated using molecular dynamics (MD) computation which reveals that substituent dimensions dictate a well-defined set of polymer conformations, in turn driving chain aggregation, and ultimately, the various film morphologies and mixing with acceptor small molecules. A straightforward energetic parameter explains the experimental polymer domain morphological trends, hence PCE, and suggests strategies for substituent selection to optimize PSC materials morphologies.

Singlet fission (SF) is a photophysical process in which one of two adjacent organic molecules absorbs a single photon, resulting in rapid formation of a correlated triplet pair (T(1)T(1)) state whose spin dynamics influence the successful generation of uncorrelated triplets (T(1)). Femtosecond transient visible and near-infrared absorption spectroscopy of a linear terrylene-3,4:11,12-bis(dicarboximide) dimer (TDI(2)), in which the two TDI molecules are directly linked at one of their imide positions, reveals ultrafast formation of the (T(1)T(1)) state. The spin dynamics of the (T(1)T(1)) state and the processes leading to uncoupled triplets (T(1)) were studied at room temperature for TDI(2) aligned in 4-cyano-4′-pentylbiphenyl (5CB), a nematic liquid crystal. Time-resolved electron paramagnetic resonance spectroscopy shows that the (T(1)T(1)) state has mixed (5)(T(1)T(1)) and (3)(T(1)T(1)) character at room temperature. This mixing is magnetic field dependent, resulting in a maximum triplet yield at ∼200 mT. The accessibility of the (3)(T(1)T(1)) state opens a pathway for triplet–triplet annihilation that produces a single uncorrelated T(1) state. The presence of the (5)(T(1)T(1)) state at room temperature and its relationship with the (1)(T(1)T(1)) and (3)(T(1)T(1)) states emphasize that understanding the relationship among different (T(1)T(1)) spin states is critical for ensuring high-yield T(1) formation from singlet fission.

The electrochemical reduction of the Mn(bpy)(CO)3X CO2 reduction catalyst is thought to proceed by the initial reduction of MnI to Mn0. We have covalently attached a naphthalenediimide radical anion (NDI•–) chromophore to the 4-, 5-, or 6-position of the bpy via a phenyl bridge to produce Mn(NDI•–-bpy)(CO)3X, where X = Br, CH3CN, or DMF, and have used femtosecond and nanosecond transient IR spectroscopy to directly observe the intermediates produced by two electron-transfer reactions following selective photoexcitation of NDI•– to its lowest excited doublet state, 2*NDI•–. In complexes where NDI•– is attached at the 4- or 5-position of bipyridine, only the reaction Mn(2*NDI•–-bpy)(CO)3X → Mn(NDI-bpy•–)(CO)3X is observed, whereas in the complex where NDI•– is attached to the 6-position of bipyridine, the reaction sequence Mn(2*NDI•–-bpy)(CO)3X → Mn(NDI-bpy•–)(CO)3X → Mn0(NDI-bpy)(CO)3 is observed. Moreover, in the complexes with an NDI•– bound to the 6-position of bipyridine, Mn0(NDI-bpy)(CO)3 exhibits a l...

The ability to prepare physical qubits in specific initial quantum states is a critical requirement for their use in quantum information science (QIS). Subnanosecond photoinduced electron transfer in a structurally well-defined donor-acceptor system can be used to produce an entangled spin qubit (radical) pair in a pure initial singlet state fulfilling this criterion. Synthetic DNA is a promising platform on which to build spin qubit arrays with fixed spatial relationships; therefore, we have prepared a series of DNA hairpins in which naphthalenediimide (NDI) is the chromophore/acceptor hairpin linker, variable-length diblock A- and G-tracts are intermediate donors, and a stilbenediether (Sd) is the terminal donor. Photoexcitation of NDI in these DNA hairpins generates high-yield, long-lived, entangled spin qubit pairs at 85 K, and time-resolved and pulse electron paramagnetic resonance (EPR) spectroscopies are used to probe their spin dynamics. Specifically, measurements of the distance-dependent dipolar coupling between the two spins are used to obtain the average spin qubit pair distance in the absence of the terminal Sd donor and reveal that one of the spins is fully delocalized across up to five adjacent guanines in a G-tract on the EPR time scale. We have recently shown that extensive spin hopping between degenerate sites accessible to one spin of the pair may result in spin decoherence. However, we observe a strong out-of-phase electron spin echo envelope modulation (OOP-ESEEM) signal from the NDI•--Sd•+ spin qubit pair in DNA hairpins showing that spin coherence is maintained across a 2 adenine A-tract followed by a 2-4 guanine G-tract as a result of rapid spin transport to Sd. These results demonstrate that pulse-EPR can manipulate coherent spin states in DNA hairpins, which is essential for quantum gate operations relevant to QIS applications.

Coherent interactions are prevalent in photodriven processes, ranging from photosynthetic energy transfer to superexchange-mediated electron transfer, resulting in numerous studies aimed towards identifying and understanding these interactions. A key motivator of this interest is the non-statistical scaling laws that result from coherently traversing multiple pathways due to quantum interference. To that end, we employed ultrafast transient absorption spectroscopy to measure electron transfer in two donor-acceptor molecular systems comprising a p-(9-anthryl)-N,N-dimethylaniline chromophore/electron donor and either one or two equivalent naphthalene-1,8:4,5-bis(dicarboximide) electron acceptors at both ambient and cryogenic temperatures. The two-acceptor compound shows a statistical factor of 2.1 ± 0.2 rate enhancement at room temperature and a non-statistical factor of 2.6 ± 0.2 rate enhancement at cryogenic temperatures, suggesting correlated interactions between the two acceptors with the donor and with the bath modes. Comparing the charge recombination rates indicates that the electron is delocalized over both acceptors at low temperature but localized on a single acceptor at room temperature. These results highlight the importance of shielding the system from bath fluctuations to preserve and ultimately exploit the coherent interactions.

The process of singlet fission (SF) produces two triplet excited states (T1 + T1) from one singlet excited exciton (S1) and a molecule in its ground state (S0). It, thus, possesses the potential to boost the solar cell efficiency above the thermodynamic Shockley–Queisser limit of 33%. A key intermediate in the SF mechanism is the singlet correlated triplet pair state 1(T1T1). This state is of great relevance, as its formation is spin-allowed and, therefore, very fast and efficient. Three fundamentally different pathways to formation of 1(T1T1) have been documented so far. The factors that influence which mechanism is associated with which chromophore, however, remain largely unknown. In order to harvest both triplet excitons independently, a decorrelation of the correlated triplet pair state to two individual triplets is required. This second step of the SF process implies a change in the total spin quantum number. In the case of a dimer, this is usually only possible if the coupling between the two pentacenes is sufficiently weak. In this study, we present two platinum-bridged pentacene dimers in which the pentacenes are coupled strongly, so that spin-decorrelation yielding (T1 + T1) was initially expected to be outcompeted by triplet–triplet annihilation (TTA) to the ground state. Both platinum-bridged pentacene dimers undergo quantitative formation of the (T1T1) state on a picosecond timescale that is unaffected by the internal heavy-atom effect of the platinum. Instead of TTA of (T1T1) to the ground state, the internal heavy-atom effect allows for 1(T1T1)–3(T1T1) and 1(T1T1)–5(T1T1) mixing and, thus, triggers subsequent TTA to the (T1S0) state and minor formation of (T1 + T1). A combination of transient absorption and transient IR spectroscopy is applied to investigate the mechanism of the (T1T1) formation in both dimers. Using a combination of experiment and quantum chemical calculations, we are able to observe a transition from the CT-mediated to the direct SF mechanism and identify relevant factors that influence the mechanism that dominates SF in pentacene. Moreover, a combination of time-resolved optical and electron paramagnetic resonance spectroscopic data allows us to develop a kinetic model that describes the effect of enhanced spin–orbit couplings on the correlated triplet pair state.

Colored charge-transfer complexes can be formed by the association between electron-rich donor and electron-deficient acceptor molecules, bringing about the narrowing of HOMO-LUMO energy gaps so that they become capable of harnessing visible light. In an effort to facilitate the use of these widespread, but nonetheless weak, interactions for visible light photocatalysis, it is important to render the interactions strong and robust. Herein, we employ a well-known donor-acceptor [2]catenane-formed by the mechanical interlocking of cyclobis(paraquat-p-phenylene) and 1,5-dinaphtho[38]crown-10-in which the charge-transfer interactions between two 4,4'-bipyridinium and two 1,5-dioxynaphthalene units are enhanced by mechanical bonding, leading to increased absorption of visible light, even at low concentrations in solution. As a result, since this [2]catenane can generate persistent bipyridinium radical cations under continuous visible-light irradiation without the need for additional photosensitizers, it can display good catalytic activity in both photo-reductions and -oxidations, as demonstrated by hydrogen production-in the presence of platinum nanoparticles-and aerobic oxidation of organic sulfides, such as l-methionine, respectively. This research, which highlights the usefulness of nanoconfinement present in mechanically interlocked molecules for the reinforcement of weak interactions, can not only expand the potential of charge-transfer interactions in solar energy conversion and synthetic photocatalysis but also open up new possibilities for the development of active artificial molecular shuttles, switches, and machines.

The interaction of low-energy light with matter that leads to the production of high-energy light is known as photon upconversion. This phenomenon is of importance because of its potential applications in optoelectronics, energy harvesting, and the biomedical arena. Herein, we report a pillared-paddlewheel metal-organic framework (MOF), constructed from a tetrakis(4-carboxyphenyl)porphyrin sensitizer and a dipyridyl thiazolothiazole annihilator, designed for efficient triplet-triplet annihilation upconversion (TTA-UC). Single-crystal X-ray diffraction studies reveal that the Zn-metalated sensitizers are coordinated to Zn2 nodes in a paddlewheel fashion, forming 2D sheets, to which are linked annihilators, such that each sensitizer is connected to five of them. The precise arrangements of sensitizers with respect to annihilators, and the high annihilator-to-sensitizer ratio, facilitate Dexter energy transfer. This level of organization in an extended structure leads to a high TTA-UC efficiency of 1.95% (theoretical maximum = 50%) at an excitation power density of 25 mW cm-2.

The designing of tunable molecular systems that can host spin qubits is a promising strategy for advancing the development of quantum information science (QIS) applications. Photogenerated radical pairs are good spin qubit pair (SQP) candidates because they can be initialized in a pure quantum state that exhibits relatively long coherence times. DNA is a well-studied molecular system that allows for control of energetics and spatial specificity through careful design and thus serves as a tunable scaffold on which to control multispin interactions. Here, we examine a series of DNA hairpins that use naphthalenediimide (NDI) as the hairpin linker. Photoexcitation of the NDI leads to subnanosecond oxidation of guanine (G) within the duplex or a stilbenediether (Sd) end-cap to give NDI•--G•+ or NDI•--Sd•+ SQPs, respectively. A 2,2,6,6-tetramethylpiperdinyl-1-oxyl (TEMPO) stable radical is covalently attached to the hairpin at varying distances from the SQP spins. While TEMPO has a minimal effect on the SQP formation and decay dynamics, EPR spectroscopy indicates that there are significant spin-spin dipolar interactions between the SQP and TEMPO. We also demonstrate the ability to implement more complex spin manipulations of the NDI•--Sd•+-TEMPO system using pulse-EPR techniques, which is important for developing DNA hairpins for QIS applications.

Singlet fission (SF) is a photophysical process capable of boosting the efficiency of solar cells. Recent experimental investigations into the mechanism of SF provide evidence for coherent mixing between the singlet, triplet, and charge transfer basis states. Up until now, this interpretation has largely focused on electronic interactions; however, nuclear motions resulting in vibronic coupling have been suggested to support rapid and efficient SF in organic chromophore assemblies. Further information about the complex interactions between vibronic excited states is needed to understand the potential role of this coupling in SF. Here, we report mixed singlet and correlated triplet pair states giving rise to sub-50 fs SF in a terrylene-3,4:11,12-bis(dicarboximide) (TDI) dimer in which the two TDI molecules are covalently linked by a direct N-N connection at one of their imide positions, leading to a linear dimer with perpendicular TDI π systems. We observe the transfer of low-frequency coherent wavepackets between the initial predominantly singlet states to the product triplet-dominated states. This implies a non-negligible dependence of SF on nonadiabatic coupling in this dimer. We interpret our experimental results in the framework of a modified Holstein Hamiltonian, which predicts that vibronic interactions between low-frequency singlet modes and high-frequency correlated triplet pair motions lead to mixing of the pure basis states. These results highlight how nonadiabatic mixing can shape the complex potential energy landscape underlying ultrafast SF.

Quantum coherence effects on charge transfer and spin dynamics in a system having two degenerate electron acceptors are studied using a zinc 5,10,15-tri(n-pentyl)-20-phenylporphyrin (ZnP) electron donor covalently linked to either one or two naphthalene-1,8:4,5-bis(dicarboximide) (NDI) electron acceptors using an anthracene (An) spacer, ZnP-An-NDI (1) and ZnP-An-NDI2 (2), respectively. Following photoexcitation of 1 and 2 in toluene at 295 K, femtosecond transient absorption spectroscopy shows that the electron transfer (ET) rate constant for 2 is about three times larger than that of 1, which can be accounted for by the statistical nature of incoherent ET as well as the electron couplings for the charge separation reactions. In contrast, the rate constant for charge recombination (CR) of 1 is about 25% faster than that of 2. Using femtosecond transient infrared spectroscopy and theoretical analysis, we find that the electron on NDI2•- in 2 localizes onto one of the two NDIs prior to CR, thus precluding electronically coherent CR from NDI2•-. Conversely, CR in both 1 and 2 is spin coherent as indicated by the observation of a resonance in the 3*ZnP yield following CR as a function of applied magnetic field, giving spin-spin exchange interaction energies of 2J = 210 and 236 mT, respectively, where the line width of the resonance for 2 is greater than 1. These data show that while CR is a spin-coherent process, incoherent hopping of the electron between the two NDIs in 2, consistent with the lack of delocalization noted above, results in greater spin decoherence in 2 relative to 1.

We have studied two regioisomeric terrylenediimide (TDI) dimers in which the 1-positions of two TDIs are linked via 1,3- or 1,4-phenylene spacers, mTDI2 and pTDI, respectively. The nature and the dynamics of the multiexciton state are tuned by altering the through-bond electronic couplings in the ground and excited states and by changing the solvent environment. Our results show that controlling the electronic coupling between the two chromophores by an appropriate choice of linker can result in independent triplet state formation, even though the initial correlated triplet pair state is confined to a dimer. Moreover, even in polar solvents, if the electronic coupling is strong, the correlated triplet pair state is observed prior to symmetry-breaking charge separation. These results point out the close relationship between the singlet, correlated triplet pair, and charge transfer states in molecular dimers.

Generation of electron-hole pairs via symmetry-breaking charge separation (SB-CS) in photoexcited assemblies of organic chromophores is a potentially important route to enhancing the open-circuit voltage of organic photovoltaics. While most reports of SB-CS have focused on molecular dimers in solution where the environmental polarity can be manipulated, here, we investigate SB-CS in polycrystalline thin films of 1,6,7,12-tetra(phenoxy)perylene-3,4:9,10-bis(dicarboximide) having either n-octyl groups (octyl-tpPDI) or hydrogen atoms (H-tpPDI) attached to its imide nitrogen atoms. Structural analyses using various X-ray techniques reveal that while both compounds show π-π stacking in thin films, H-tpPDI is more slip-stacked than octyl-tpPDI and has intermolecular hydrogen bonds to its neighboring molecules. Transient absorption spectroscopy shows that octyl-tpPDI exhibits strong mixing between its singlet excited state and a charge transfer state, yielding an excimer-like state, while H-tpPDI undergoes nearly quantitative SB-CS, making the latter a promising candidate for use in organic photovoltaic devices.

We report the encapsulation of free-base and zinc porphyrins by a tricyclic cyclophane receptor with subnanomolar binding affinities in water. The high affinities are sustained by the hydrophobic effect and multiple [CH···π] interactions covering large [π···π] stacking surfaces between the substrate porphyrins and the receptor. We discovered two co-conformational isomers of the 1:1 complex, where the porphyrin is orientated differently inside the binding cavity of the receptor on account of its tricyclic nature. The photophysical properties and chemical reactivities of the encapsulated porphyrins are modulated to a considerable extent by the receptor. Improved fluorescence quantum yields, red-shifted absorptions and emissions, and nearly quantitative energy transfer processes highlight the emergent photophysical enhancements. The encapsulated porphyrins enjoy unprecedented chemical stabilities, where their D/H exchange, protonation, and solvolysis under extremely acidic conditions are completely blocked. We anticipate that the ultrahigh stabilities and improved optical properties of these encapsulated porphyrins will find applications in single-molecule materials, artificial photodevices, and biomedical appliances.

Efficient heterogeneous photosensitizing materials require both large accessible surface areas and excitons of suitable energies and with well-defined spin structures. Confinement of the tetracationic cyclophane (ExBox4+ ) within a nonporous anionic polystyrene sulfonate (PSS) matrix leads to a surface area increase of up to 225 m2 g-1 in ExBox•PSS. Efficient intersystem crossing is achieved by combining the spin-orbit coupling associated to Br heavy atoms in 1,3,5,8-tetrabromopyrene (TBP), and the photoinduced electron transfer in a TBP⊂ExBox4+ supramolecular dyad. The TBP⊂ExBox4+ complex displays a charge transfer band at 450 nm and an exciplex emission at 520 nm, indicating the formation of new mixed-electronic states. The lowest triplet state (T1 , 1.89 eV) is localized on the TBP and is close in energy with the charge separated state (CT, 2.14 eV). The homogeneous and heterogeneous photocatalytic activities of the TBP⊂ExBox4+ , for the elimination of a sulfur mustard simulant, has proved to be significantly more efficient than TBP and ExBox+4 , confirming the importance of the newly formed excited-state manifold in TBP⊂ExBox4+ for the population of the low-lying T1 state. The high stability, facile preparation, and high performance of the TBP⊂ExBox•PSS nanocomposites augur well for the future development of new supramolecular heterogeneous photosensitizers using host-guest chemistry.

The KLHL14 gene acquires frequent inactivating mutations in mature B cell malignancies, especially in the MYD88 L265P , CD79B mutant (MCD) genetic subtype of diffuse large B cell lymphoma (DLBCL), which relies on B cell receptor (BCR) signaling for survival. However, the pathogenic role of KLHL14 in DLBCL and its molecular function are largely unknown. Here, we report that KLHL14 is in close proximity to the BCR in the endoplasmic reticulum of MCD cell line models and promotes the turnover of immature glycoforms of BCR subunits, reducing total cellular BCR levels. Loss of KLHL14 confers relative resistance to the Bruton tyrosine kinase (BTK) inhibitor ibrutinib and promotes assembly of the MYD88-TLR9-BCR (My-T-BCR) supercomplex, which initiates prosurvival NF-κB activation. Consequently, KLHL14 inactivation allows MCD cells to maintain NF-κB signaling in the presence of ibrutinib. These findings reinforce the central role of My-T-BCR–dependent NF-κB signaling in MCD DLBCL and suggest that the genetic status of KLHL14 should be considered in clinical trials testing inhibitors of BTK and BCR signaling mediators in DLBCL.

An octacationic diazaperopyrenium (DAPP2+)-based homo[2]catenane (DAPPHC8+), wherein no fewer than eight positive charges are associated within a mechanically interlocked molecule, has been produced in 30% yield under ambient conditions as a result of favorable homophilic interactions, reflecting a delicate balance between strong π–π interactions and the destabilizing penalty arising from Coulombic repulsions between DAPP2+ units. This DAPPHC8+ catenane is composed of two identical mechanically interlocked tetracationic cyclophanes, namely DAPPBox4+, each of which contains one DAPP2+ unit and one extended viologen (ExBIPY2+) unit, linked together by two p-xylylene bridges. The solid-state structure of the homo[2]catenane demonstrates how homophilic interactions play an important role in the formation of DAPPHC8+, in which the mean ring planes of the two DAPPBox4+ cyclophanes are oriented at about 60° with respect to each other, with a centroid-to-centroid separation of 3.7 A between the mean planes of the...

Summary Singlet fission (SF) is a process that converts one singlet excited state into two triplet states. The mechanism of SF is still not well understood. Here, we report on the use of a combination of transient absorption and electron paramagnetic resonance spectroscopies in conjunction with theoretical calculations to probe SF in a pentacene dimer linked by a non-conjugated, 1,4-diethynylbicyclo[2.2.2]octane spacer. Next to observing the key intermediates in solution-based SF, including the formation and decay of a quintet state that precedes formation of the pentacene triplet excitons, we demonstrate that the coupling is sufficiently weak that SF is essentially inoperative in non-polar media. Transitioning to a polar medium, however, amplifies the coupling strength such that SF becomes operative and supports long triplet lifetimes. Our results offer strong evidence for a charge-transfer mediation and, in turn, provide a solid framework for decoding the complete mechanism of SF in systems beyond pentacene.

Controlling spin–spin interactions in multispin molecular assemblies is important for developing new approaches to quantum information processing. In this work, a covalent electron donor–acceptor–radical triad is used to probe spin-selective reduction of the stable radical to its diamagnetic anion. The molecule consists of a perylene electron donor chromophore (D) bound to a pyromellitimide acceptor (A), which is, in turn, linked to a stable α,γ-bisdiphenylene-β-phenylallyl radical (R•) to produce D-A-R•. Selective photoexcitation of D within D-A-R• results in ultrafast electron transfer to form the D+•-A–•-R• triradical, where D+•-A–• is a singlet spin-correlated radical pair (SCRP), in which both SCRP spins are uncorrelated relative to the R• spin. Subsequent ultrafast electron transfer within the triradical forms D+•-A-R–, but its yield is controlled by spin statistics of the uncorrelated A–•-R• radical pair, where the initial charge separation yields a 3:1 statistical mixture of D+•-3(A–•-R•) and D+•-...

Facile exciton transport within ordered assemblies of π-stacked chromophores is essential for developing molecular photonic and electronic materials. Excimer states having variable charge transfer (CT) character are frequently implicated as promoting or inhibiting exciton mobility in such systems. However, determining the degree of CT character in excimers as a function of their structure has proven challenging. Herein, we report on a series of cyclophanes in which the interplanar distance between two phenyl-extended viologen (ExV2+) chromophores is varied systematically using a pair of o-, m-, or p-xylylene (o-, m-, or p-Xy) covalent linkers to produce o-ExBox4+ (3.5 A), m-ExBox4+ (5.6 A), and p-ExBox4+ (7.0 A), respectively. The cyclophane structures are characterized using NMR spectroscopy in solution and single-crystal X-ray diffraction in the solid state. Femtosecond transient mid-IR and stimulated Raman spectroscopies show that the CT contribution to the excimer states formed in o-ExBox4+ and m-ExBox4+ depends on the distance between the chromophores within the cyclophanes, while in the weak interaction limit, as represented by p-ExBox4+ (7.0 A), the lowest excited singlet state of ExV2+ exclusively photo-oxidizes the p-Xy spacer to give the p-Xy+•-ExV+• ion pair. Moreover, the vibrational spectra of the excimer state show that it assumes a geometry that is intermediate between that of the locally excited and CT states, approximately reflecting the degree of CT character.

Cyano-substituted tetracenes (5,11-dicyano-6,12-diphenyltetracene, Tet) undergo exoergic singlet fission (SF), a spin-allowed photophysical process that generates a pair of triplet excitons from one singlet exciton. To elucidate substituent effects on SF, we have measured the SF dynamics and triplet yields of thin films, formed by Tet bearing hydrogen (H), methyl (Me), fluoro (F), and trimethylsilyl (TMS) substituents on the p-phenyl positions and on the 3 and 9 positions of the tetracene core, by time-resolved spectroscopy in the vis-NIR and IR regions. The H-, Me-, and F-Tet display strong intramolecular electronic coupling (π–π distances 4 Å) reduces its SF triplet yield to about 60%.

Molecules capable of performing highly efficient energy transfer and ultrafast photo-induced electron transfer in well-defined multichromophoric structures are indispensable to the development of artificial photosynthetic systems. Herein, we report on the synthesis, characterization and photophysical properties of a rationally designed multichromophoric tetracationic cyclophane, DAPPBox^(4+), containing a diazaperopyrenium (DAPP^(2+)) unit and an extended viologen (ExBIPY^(2+)) unit, which are linked together by two p-xylylene bridges. Both ^1H NMR spectroscopy and single crystal X-ray diffraction analysis confirm the formation of an asymmetric, rigid, box-like cyclophane, DAPPBox^(4+). The solid-state superstructure of this cyclophane reveals a herringbone-type packing motif, leading to two types of π···π interactions: (i) between the ExBIPY^(2+) unit and the DAPP^(2+) unit (π···π distance of 3.7 Å) in the adjacent parallel cyclophane, as well as (ii) between the ExBIPY^(2+) unit (π···π distance of 3.2 Å) and phenylene ring in the closest orthogonal cyclophane. Moreover, the solution-phase photophysical properties of this cyclophane have been investigated by both steady-state and time-resolved absorption and emission spectroscopies. Upon photoexcitation of DAPPBox^(4+) at 330 nm, rapid and quantitative intramolecular energy transfer occurs from the ^1*ExBIPY^(2+) unit to the DAPP^(2+) unit in 0.5 ps to yield ^1*DAPP^(2+). The same excitation wavelength simultaneously populates a higher excited state of ^1*DAPP^(2+) which then undergoes ultrafast intramolecular electron transfer from ^1*DAPP^(2+) to ExBIPY^(2+) to yield the DAPP^(3+•) – ExBIPY^(+•) radical ion pair in τ = 1.5 ps. Selective excitation of DAPP^(2+) at 505 nm populates a lower excited state where electron transfer is kinetically unfavorable.

Photodriven electron transfer from a donor excited state to an assembly of electronically coupled acceptors has been proposed to enhance charge transfer efficiency in functional organic electronic materials. However, the circumstances under which this may occur are difficult to investigate in a controlled manner in disordered donor–acceptor materials. Here we investigate the effects of anion delocalization on electron transfer using zinc meso-tetraphenylporphyrin (ZnTPP) as a donor and a perylene-3,4:9,10-bis(dicarboximide) dimer as the acceptor (PDI2). The PDI units of the dimer are positioned in a cofacial orientation relative to one another by attachment of the imide group of each PDI to the 4- and 5-positions of a xanthene spacer. Furthermore, the distal imide group of one PDI is linked to the para-position of one ZnTPP phenyl group to yield ZnTPP-PDI2. The data for the dimer are compared to two different ZnTPP-PDI monomer reference systems designed to probe electron transfer to each of the individual PDI molecules comprising PDI2. The electron transfer rate from the ZnTPP lowest excited singlet state to PDI2 is increased by 50% relative to that in ZnTPP-PDI, when the data are corrected for the statistics of having two electron acceptors. Femtosecond transient IR absorption spectroscopy provides evidence that the observed enhancement in charge separation results from electron transfer producing a delocalized PDI2 anion.

A major goal of artificial photosynthesis research is photosensitizing highly reducing metal centers using as much as possible of the solar spectrum reaching Earth's surface. The radical anions and dianions of rylenediimide (RDI) dyes, which absorb at wavelengths as long as 950 nm, are powerful photoreductants with excited state oxidation potentials that rival or exceed those of organometallic chromophores. These dyes have been previously incorporated into all-organic donor–acceptor systems, but have not yet been shown to reduce organometallic centers. This study describes a set of dyads in which perylenediimide (PDI) or naphthalenediimide (NDI) chromophores are attached to Re(bpy)(CO)3 through either the bipyridine ligand or more directly to the Re center via a pyridine ligand. The chromophores are reduced with a mild reducing agent, after which excitation with long-wavelength red or near-infrared light leads to reduction of the Re complex. The kinetics of electron transfer from the photoexcited anions to the Re complex are monitored using transient visible/near-IR and mid-IR spectroscopy, complemented by theoretical spectroscopic assignments. The photo-driven charge shift from the reduced PDI or NDI to the complex occurs in picoseconds regardless of whether PDI or NDI is attached to the bipyridine or to the Re center, but back electron transfer is found to be three orders of magnitude slower with the chromophore attached to the Re center. These results will inform the design of future catalytic systems that incorporate RDI anions as chromophores.

Singlet exciton fission (SF) in organic chromophore assemblies results in the conversion of one singlet exciton (S1) into two triplet excitons (T1), provided that the overall process is exoergic, i.e., E(S1) > 2E(T1). We report on SF in thin polycrystalline films of two terrylene-3,4:11,12-bis(dicarboximide) (TDI) derivatives 1 and 2, which crystallize into two distinct π-stacked structures. Femtosecond transient absorption spectroscopy (fsTA) reveals a charge-transfer state preceding a 190% T1 yield in films of 1, where the π-stacked TDI molecules are rotated by 23° along an axis perpendicular to their π systems. In contrast, when the TDI molecules are slip-stacked along their N–N axes in films of 2, fsTA shows excimer formation, followed by a 50% T1 yield.

The efficiency and dynamics of hole transport via base mismatches and strand crossings have been determined for 10 DNA hairpins by means of femtosecond transient absorption spectroscopy. The hairpins possess a stilbenedicarboxamide hole donor and stilbenediether hole acceptor separated by seven base pairs. Hole transport occurs via an intra- or interstrand A 3 G 4 diblock purine sequence that contains either a single base pair mismatch or strand crossing. Pyrimidine-pyrimidine mismatches (TT or CC) effectively block intrastrand hole transport; whereas purine-purine mismatches (AA or GG) permit efficient interstrand hole transport. Purine-to-purine intrastrand hole transport between adjacent matched base pairs is also moderately efficient (AG > AA > GG). Based upon these results AA mismatches are being employed in the design of three-way junctions for incorporation in prototype charge splitting and charge combining devices.

We investigate backbone fluorination effects in bulk-heterojunction (BHJ) polymer solar cells (PSCs) with the fluorine-poor PBDTT-FTTE and fluorine-rich PBDTTF-FTTE donor polymers, paired with the ...

Singlet fission (SF) converts a singlet exciton into two triplet excitons in two or more electronically coupled organic chromophores, which may then be used to increase solar cell efficiency. Many known SF chromophores are unsuitable for device applications due to chemical instability or low triplet state energies. The results described here show that efficient SF occurs in derivatives of 9,10-bis(phenylethynyl)anthracene (BPEA), which is a highly robust and tunable chromophore. Fluoro and methoxy substituents at the 4- and 4′-positions of the BPEA phenyl groups control the intermolecular packing in the crystal structure, which alters the interchromophore electronic coupling, while also changing the SF energetics. The lowest excited singlet state (S1) energy of 4,4′-difluoro-BPEA is higher than that of BPEA so that the increased thermodynamic favorability of SF results in a (16 ± 2 ps)−1 SF rate and a 180% ± 16% triplet yield, which is about an order of magnitude faster than BPEA with a comparable triplet yield. By contrast, 4-fluoro-4′-methoxy-BPEA and 4,4′-dimethoxy-BPEA have slower SF rates, (90 ± 20 ps)−1 and (120 ± 10 ps)−1, and lower triplet yields, (110 ± 4)% and (168 ± 7)%, respectively, than 4,4′-difluoro-BPEA. These differences are attributed to changes in the crystal structure controlling interchromophore electronic coupling as well as SF energetics in these polycrystalline solids.

When a molecular electron donor interacts with multiple electron acceptors, quantum coherence can enhance the electron transfer (ET) rate. Here we report photodriven ET rates in a pair of donor–acceptor (D-A) compounds that link one anthracene (An) donor to one or two equivalent 1,4-benzoquinone (BQ) acceptors. Subpicosecond ET from the lowest excited singlet state of An to two BQs is about 2.4 times faster than ET to one BQ at room temperature, but about 5 times faster at cryogenic temperatures. This factor of 2 increase results from a transition from ET to one of two acceptors at room temperature to ET to a superposition state of the two acceptors with correlated system–bath fluctuations at low temperature.

Prompted by a knowledge of the photoprotective mechanism operating in photosystem supercomplexes and bacterial antenna complexes by pigment binding proteins, we have appealed to a boxlike synthetic receptor (ExBox·4Cl) that binds a photosensitizer, 5,15-diphenylporphyrin (DPP), to provide photoprotection by regulating light energy. The hydrophilic ExBox4+ renders DPP soluble in water and modulates the phototoxicity of DPP by trapping it in its cavity and releasing it when required. While trapping removes access to the DPP triplet state, a pH-dependent release of diprotonated DPP (DPPH22+) restores the triplet deactivation pathway, thereby activating its ability to generate reactive oxygen species. We have employed the ExBox4+-bound DPP complex (ExBox4+⊃DPP) for the safe delivery of DPP into the lysosomes of cancer cells, imaging the cells by utilizing the fluorescence of the released DPPH22+ and regulating photodynamic therapy to kill cancer cells with high efficiency.

Recent advances in two-dimensional electronic spectroscopy (2DES) have enabled identification of fragile quantum coherences in condensed-phase systems near the equilibrium molecular geometry. In general, traditional 2DES cannot measure such coherences associated with photophysical processes that occur at times significantly after the initially prepared state has dephased, such as the evolution of the initial excited state into a charge transfer state. We demonstrate the use of transient two-dimensional electronic spectroscopy (t-2DES) to probe coherences in an electron donor–acceptor dyad consisting of a perylenediimide (PDI) acceptor and a perylene (Per) donor. An actinic pump pulse prepares the lowest excited singlet state of PDI followed by formation of the PDI•––Per•+ ion pair, which is probed at different times following the actinic pulse using 2DES. Analysis of the observed coherences provides information about electronic, vibronic, and vibrational interactions at any time along the reaction coordinate for ion pair formation.

Achieving high-yielding photoinduced charge separation through the π-stacked bases of DNA is a critical requirement for realizing numerous DNA-based technologies. In the current work, we combine two strategies for achieving high-yield charge separation. First, a chromophore with a high driving force for charge injection, naphthalenediimide (NDI), is used because it generates hot carriers that enhance charge-transfer rates. Second, a diblock DNA sequence is used with two or three adenines followed by a series of guanines to implement an energy landscape that accelerates charge separation while retarding charge recombination. The photoinduced dynamics of these NDI diblock oligomers with and without a terminal hole acceptor are probed by femtosecond transient absorption spectroscopy. The measured rate constants for various charge separation and recombination processes are interpreted within the context of a full kinetic model of these systems. We find that the A