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The total photon economy of a chromophore molecular species represents a study of how absorbed photons partition among various electronic states and ultimately dissipate their excited energy into the environment. A complete accounting of these rates and pathways would allow one to optimize chromophores and their environments for applications. We describe a technique, fluorescent optical cycling (FOC), which allows for simultaneous observation of prompt and delayed emission during and after multiple pulsed excitation, ultimately granting access to multi-state photophysical rates. We exercise control over the excitation pulse train, which allows us to "optically shelve" long-lived intermediate states without the use of diode or flashlamp excitation. By recording all photon arrival times in the visible and shortwave infrared, we can simultaneously resolve fluorescence, phosphorescence, and singlet oxygen sensitization in a single experiment. We use FOC to examine the photophysics of dual emitting bis(di-R-phosphino)alkanethiophene-pyridine-platinum ([Pt(thpy)(dppm)]+) under different solvation conditions, revealing changes in intersystem crossing and phosphorescent rates induced by the external heavy atom effect. Coupling FOC with decay associated Fourier spectroscopy (DAFS), we demonstrate simultaneous correlated spectral and lifetime data in this dual emitting complex. Finally, FOC combined with superconducting nanowire single photon detectors (SNSPDs) allows us to observe the shortwave infrared region (SWIR) phosphorescence of singlet oxygen sensitized by Rose Bengal. Overall, FOC provides a powerful tool to simultaneously study multiple photophysics across timescales, even in weakly populated electronic states.
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Due to the expanding applications of icosahedral carboranes in medicinal and materials chemistry research, their functionalizations have become one of the central themes in boron-rich cluster chemistry. Although several strategies for incorporating nitrogen-containing nucleophiles on a single boron vertex of the icosahedral carboranes (C2B10H12) have been developed, methods for preparing clusters with vicinal B-N moieties are still lacking. The steric bulk of icosahedral carboranes and disparate electronic and steric nature of the N-containing groups have rendered the vicinal diamination challenging. In this article, we show how a developed Pd-catalyzed process is used to incorporate an array of NH-heterocycles, anilines, and heteroanilines with various electronic and steric profiles onto the vicinal boron vertices of a meta-carborane cluster via sequential or one-pot fashion. Importantly, oxidative cyclizations of the cross-coupling products with indoles and pyrroles appended to boron vertices generate a previously unknown class of all-boron-vertex bound carborane-fused six- and seven-membered ring heterocycles. Photophysical studies of the meta-carborane-fused heterocycles show that these structures can exhibit luminescence with high quantum yields and are amenable to further manipulations.
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Conjugated polymers are a versatile class of electronic materials featured in a variety of next-generation electronic devices. The utility of such polymers is contingent in large part on their electrical conductivity, which depends both on the density of charge carriers (polarons) and on the carrier mobility. Carrier mobility, in turn, is largely controlled by the separation between the polarons and dopant counterions, as counterions can produce Coulombic traps. In previous work, we showed that large dopants based on dodecaborane (DDB) clusters were able to reduce Coulombic binding and thus increase carrier mobility in regioregular (RR) poly(3-hexylthiophene-2,5-diyl) (P3HT). Here, we use a DDB-based dopant to study the effects of polaron-counterion separation in chemically doped regiorandom (RRa) P3HT, which is highly amorphous. X-ray scattering shows that the DDB dopants, despite their large size, can partially order the RRa P3HT during doping and produce a doped polymer crystal structure similar to that of DDB-doped RR P3HT; Alternating Field (AC) Hall measurements also confirm a similar hole mobility. We also show that use of the large DDB dopants successfully reduces Coulombic binding of polarons and counterions in amorphous polymer regions, resulting in a 77% doping efficiency in RRa P3HT films. The DDB dopants are able to produce RRa P3HT films with a 4.92 S/cm conductivity, a value that is â¼200× higher than that achieved with 3,5,6-tetrafluoro-7,7,8,8-tetracyanoquinodimethane (F4TCNQ), the traditional dopant molecule. These results show that tailoring dopants to produce mobile carriers in both the amorphous and semicrystalline regions of conjugated polymers is an effective strategy for increasing achievable polymer conductivities, particularly in low-cost polymers with random regiochemistry. The results also emphasize the importance of dopant size and shape for producing Coulombically unbound, mobile polarons capable of electrical conduction in less-ordered materials.
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Development of bioconjugation strategies to efficiently modify biomolecules is of key importance for fundamental and translational scientific studies. Cysteine S-arylation is an approach which is becoming more popular due to generally rapid kinetics and high chemoselectivity, as well as the strong covalently bonded S-aryl linkage created in these processes. Organometallic approaches to cysteine S-arylation have been explored that feature many advantages compared to their more traditional organic counterparts. In this Viewpoint, progress in the use of Au(III) and Pd(II) oxidative addition (OA) complexes for stoichiometric cysteine S-arylation is presented and discussed. A focus is placed on understanding the rapid kinetics of these reactions under mild conditions, as well as the ability to generate biomolecular heterostructures. Potential avenues for further exploration are addressed and usefulness of these methods to the practitioner are emphasized in the discussion.
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Cisteína , Oxidación-Reducción , Paladio , Cisteína/química , Oro/química , Cinética , Compuestos Organometálicos/química , Paladio/químicaRESUMEN
Bioconjugation of polymers to proteins is a method to impart improved stability and pharmacokinetic properties to biologic systems. However, the precise effects of polymer architecture on the resulting bioconjugates are not well understood. Particularly, cyclic polymers are known to possess unique features such as a decreased hydrodynamic radius when compared to their linear counterparts of the same molecular weight, but have not yet been studied. Here, we report the first bioconjugation of a cyclic polymer, poly(ethylene glycol) (PEG), to a model protein, T4 lysozyme, containing a single engineered cysteine residue (V131C). We compare the stability and activity of this conjugate with those of a linear PEG-T4 lysozyme analogue of similar molecular weight. Furthermore, we used molecular dynamics (MD) simulations to determine the behavior of the polymer-protein conjugates in solution. We introduce cyclic polymer-protein conjugates as potential candidates for the improvement of biologic therapeutics.
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Simulación de Dinámica Molecular , Muramidasa , Polietilenglicoles , Polietilenglicoles/química , Muramidasa/química , Bacteriófago T4/enzimologíaRESUMEN
Through mechanistic work and rational design, we have developed the fastest organometallic abiotic Cys bioconjugation. As a result, the developed organometallic Au(III) bioconjugation reagents enable selective labeling of Cys moieties down to picomolar concentrations and allow for the rapid construction of complex heterostructures from peptides, proteins, and oligonucleotides. This work showcases how organometallic chemistry can be interfaced with biomolecules and lead to a range of reactivities that are largely unmatched by classical organic chemistry tools.
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Cisteína , Oro , Cisteína/química , Oro/química , Péptidos/química , Compuestos Orgánicos de Oro/química , Compuestos Orgánicos de Oro/síntesis química , Estructura MolecularRESUMEN
ConspectusIn this Account, we discuss our group's research over the past decade on a class of functionalized boron clusters with tunable chemical and physical properties, with an emphasis on accessing and controlling their redox behavior. These clusters can be thought of as three-dimensional aromatic systems that have distinct redox behavior and photophysical properties compared to their two-dimensional organic counterparts. Specifically, our lab has studied the highly tunable, multielectron redox behavior of B12(OR)12 clusters and applied these molecules in various settings. We first discuss the spectroscopic and electrochemical characterization of B12(OR)12 clusters in various oxidation states, followed by their use as catholytes and/or anolytes in redox flow batteries and chemical dopants in conjugated polymers. Additionally, the high oxidizing potential and visible light-absorbing nature of fluoroaryl-functionalized B12(OR)12 clusters have been leveraged by our group to generate weakly coordinating, photoexcitable species that can promote photooxidation chemistry.We have further translated these solution-phase studies of B12(OR)12 clusters to the solid state by using the precursor [B12(OH)12]2- cluster as a robust building block for hybrid metal oxide materials. Specifically, we have shown that the boron cluster can act as a thermally stable cross-linking material, which enhances electron transport between metal oxide nanoparticles. We applied this structural motif to create TiO2- and WO3-containing materials that showed promising properties as photocatalysts and electroactive materials for supercapacitors. Building on this concept, we later discovered that B12(OCH3)12, the smallest of the B12(OR)12 family, could retain its redox behavior in the solid state, a previously unseen phenomenon. We successfully harnessed this unique behavior for solid-state energy storage by implementing this boron cluster as a cathode-active material in a Li-ion prototype cell device. Recently, our group has also explored how to tune the redox properties of clusters other than B12(OR)12 species by synthesizing a library of vertex-differentiated clusters containing both B-OR and B-halogen groups. Due to the additive qualities of different functional groups on the cluster, these species allow access to a region of electrochemical potentials previously inaccessible by fully substituted closo-dodecaborate alkoxy-based derivatives.Lastly, we discuss our research into smaller-sized redox-active polyhedral boranes (B6- and B10-based cluster cores). Interestingly, these clusters show significantly less redox stability and reversibility than their dodecaborate-based counterparts. While exploring the functionalization of closo-hexaborate to create fully substituted derivates (i.e., [B6R6Hfac]-), we observed unique oxidative decomposition pathways for this cluster system. Consequently, we leveraged this oxidative instability to generate useful alkyl boronate esters via selective chemical oxidation. We further explored a closo-decaborate cluster as a platform to access electrophilic [B10H13]+ species capable of directly borylating arene compounds with unique regioselectivity. Upon chemical oxidation of the arylated decaborate clusters, we successfully synthesized various aryl boronate esters, establishing the generality of the oxidative cluster deconstruction concept.Overall, our work shows that boron clusters are an appealing class of redox-active molecules, and this fundamental and understudied property can be leveraged for constructing novel materials with tunable physical and electrochemical properties, as well as producing unique chemical reagents for small molecule synthesis.
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High-performance semiconductor materials and devices are needed to supply the growing energy and computing demand. Organic semiconductors (OSCs) are attractive options for opto-electronic devices, due to their low cost, extensive tunability, easy fabrication, and flexibility. Semiconducting single-walled carbon nanotubes (s-SWCNTs) have been extensively studied due to their high carrier mobility, stability and opto-electronic tunability. Although molecular charge transfer doping affords widely tunable carrier density and conductivity in s-SWCNTs (and OSCs in general), a pervasive challenge for such systems is reliable measurement of charge carrier density and mobility. In this work we demonstrate a direct quantification of charge carrier density, and by extension carrier mobility, in chemically doped s-SWCNTs by a nuclear magnetic resonance approach. The experimental results are verified by a phase-space filling doping model, and we suggest this approach should be broadly applicable for OSCs. Our results show that hole mobility in doped s-SWCNT networks increases with increasing charge carrier density, a finding that is contrary to that expected for mobility limited by ionized impurity scattering. We discuss the implications of this important finding for additional tunability and applicability of s-SWCNT and OSC devices.
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Herein, we describe the synthesis of bench-stable organometallic Au(III) terminated polymer reagents. These reagents mediate the chemoselective S-arylation of thiol-containing small molecules and polymers to yield functionalized mono-telechelic polymers and diblock copolymers, respectively. These transformations proceed rapidly within minutes and produce conjugates in quantitative conversion, making this strategy a robust addition to the polymer functionalization toolbox.
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We report the synthesis and characterization of various compounds containing the 1,7,9-hydroxylated closo-dodecahydrododecaborate (B12H9(OH)32-) cluster motif. Specifically, we show how the parent compound can be synthesized on the multigram scale and further perhalogenated, leading to a new class of vertex-differentiated weakly coordinating anions. We show that a postmodification of the hydroxyl groups by alkylation affords further opportunities for tailoring these anions' stability, steric bulk, and solubility properties. The resulting dodecaborate-based salts were subjected to a full thermal and electrochemical stability evaluation, showing that many of these anions maintain thermal stability up to 500 °C and feature no redox activity below â¼1 V vs Fc/Fc+. Mixed hydroxylated/halogenated clusters show enhanced solubility compared to their purely halogenated analogs and retain weakly coordinating properties in the solid state, as demonstrated by ionic conductivity measurements of their Li+ salts.
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This work demonstrates the first successful electrochemical cycling of a redox-active boron cluster-based material in the solid state. Specifically, we designed and synthesized an ether-functionalized dodecaborate cluster, B12(OCH3)12, which is the smallest redox-active building block in the B12(OR)12 family. This species can reversibly access four oxidation states in solution, ranging from a dianion to a radical cation. We show that a chemically isolated and characterized neutral [B12(OCH3)12]0 cluster can be utilized as a cathode active material in a PEO-based rechargeable all-solid-state cell with a lithium metal anode. The cell exhibits an impressive active material utilization close to 95% at C/20 rate, a high Coulombic efficiency of 96%, and reversibility, with only 4% capacity fade after 16 days of cycling. This work represents a conceptual departure in the development of redox-active components for electrochemical storage and serves as an entry point to a broader class of borane-based materials.
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Introducing a tri-coordinate boron-based functional group (e.g., boronic ester) into an unactivated C-H bond in the absence of directing groups is an ongoing challenge in synthetic chemistry. Despite previous developments in transition metal-catalyzed and -free approaches, C-H borylation of sterically hindered arenes remains a largely unsolved problem to date. Here, we report a synthetic strategy of a two-step, precious metal-free electrophilic C-H borylation of sterically hindered alkyl- and haloarenes to generate aryl boronic esters. The first step relies on electrophilic aromatic substitution (EAS) induced by cage-opening of Cs2[closo-B10H10], forming a 6-Ar-nido-B10H13 product containing a B-C bond, followed by a cage deconstruction of arylated decaboranes promoted by diols. The combination of these two steps allows for the preparation of aryl boronic esters that are hardly accessible by current direct C-H borylation approaches. This reaction does not require any precious metals, highly-engineered ligands, pre-functionalized boron reagents, or inert conditions. In addition, the unique properties of a non-classical boron cluster electrophile intermediate, B10H13+, afford a regioselectivity with unique steric and electronic control without the undesirable side reactions.
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In this work, two pathways of reactivity are investigated to generate site-specific substitutions at the B7 vertex of the luminescent boron cluster, anti-B18H22. First, a palladium-catalyzed cross-coupling reaction utilizing the precursor 7-I-B18H21 and a series of model nucleophiles was developed, ultimately producing several B-N- and B-O-substituted species. Interestingly, the B-I bond in this cluster can also be substituted in an uncatalyzed fashion, leading to the formation of various B-N, B-O, and B-S products. This work highlights intricate differences corresponding to these two reaction pathways and analyzes the role of solvents and additives on product distributions. As a result of our synthetic studies, seven new B18-based clusters were synthesized, isolated, and characterized by mass spectrometry and nuclear magnetic resonance (NMR) spectroscopy. The photoluminescence properties of two structurally similar ether and thioether products were further investigated, with both exhibiting blue fluorescence in solution at 298 K and long-lived green or yellow phosphorescence at 77 K. Overall, this work shows, for the first time, the ability to perform substitution of a boron-halogen bond with nucleophiles in a B18-based cluster, resulting in the formation of photoluminescent molecules.
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Boro , Paladio , Boro/química , Catálisis , Éter , Halógenos , Paladio/química , Solventes/química , Sulfuros/químicaRESUMEN
Bioconjugation techniques for biomolecule-polymer conjugation are numerous; however, slow kinetics and steric challenges generally necessitate excess reagents or long reaction times. Organometallic transformations are known to circumvent these issues; yet, harsh reaction conditions, incompatibility in aqueous media, and substrate promiscuity often limit their use in a biological context. The work reported herein demonstrates a facile and benign organometallic Au(III) S-arylation approach that enables the synthesis of poly(ethylene glycol) monomethyl ether (mPEG)-protein conjugates with high efficiency. Isolable and bench-stable 2, 5, and 10 kDa mPEG-Au(III) reagents were synthesized via oxidative addition into terminal aryl iodide substituents installed on mPEG substrates with a (Me-DalPhos)Au(I)Cl precursor. Reaction of the isolable mPEG-Au(III) oxidative addition complexes with a cysteine thiol on a biomolecule resulted in facile and selective cysteine arylation chemistry, forging covalent S-aryl linkages and affording the mPEG-biomolecule conjugates. Notably, low polymer reagent loadings were used to achieve near quantitative conversion at room temperature in 1 min due to the rapid kinetics and high chemoselectivity of this Au-based bioconjugation approach. Therefore, this work represents an important addition to the protein-polymer conjugation chemical toolbox.
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Cisteína , Polietilenglicoles , Cisteína/química , Indicadores y Reactivos , Oxidación-Reducción , Polietilenglicoles/química , Proteínas/químicaRESUMEN
In this work, we discuss the synthesis and characterization of a 2D coordination polymer composed of a dianionic perhydroxylated boron cluster, [B12(OH)122-], coordinated to Zn(II)-the first example of a transition metal-coordinated [B12(OH)12]2- compound. This material was synthesized via cation exchange from the starting cesium salt and then subjected to rigorous characterization prior to and after thermal activation. Numerous techniques, including XRD, FTIR, SEM, TGA, and solid-state NMR revealed a 2D coordination polymer composed of sheets of Zn(II) ions intercalated between planes of boron clusters. The as-synthesized material was then evacuated of solvent via thermal treatment, and atomic-level changes from this transformation were elucidated through a combination of 1D and 2D solid-state NMR analyses of 11B and 1H nuclei, suggesting the full removal of coordinated solvent molecules. Evidence also suggested that [B12(OH)122-] can adjust its coordination to Zn(II) in the solid-state through hemilability of its numerous -OH ligands.
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The 18F labeling of unprotected peptides and sugars with a Au(III)-[18F]fluoroaryl complex is reported. The chemoselective method generates 18F-labeled S-aryl bioconjugates in an aqueous environment in 15 min with high radiochemical yields and displays excellent functional group tolerance. This approach utilizes an air and moisture stable, robust organometallic Au(III) complex and highlights the versatility of designer organometallic reagents as efficient agents for rapid radiolabeling.
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Radioisótopos de Flúor , Oro , Marcaje Isotópico , Péptidos , Radiofármacos , AzúcaresRESUMEN
The dynamic photoluminescence properties, and potential quenching mechanisms, of anti-B18H22, 4,4'-Br2-anti-B18H20, and 4,4'-I2-anti-B18H20 are investigated in solution and polymer films. UV stability studies of the neat powders show no decomposition occurring after intense 7 day light soaking. In contrast, clusters incorporated into polymer films are found to degrade into smaller borane fragments under the same irradiation conditions. To highlight the utility of these compounds, we leverage their favorable optical properties in a prototype UV imaging setup.
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Chalcogen-containing carboranes have been known for several decades and possess stable exopolyhedral B(9)-Se and B(9)-Te σ bonds despite the electron-donating ability of the B(9) vertex. While these molecules are known, little has been done to thoroughly evaluate their electrophilic and nucleophilic behavior. Herein, we report an assessment of the electrophilic reactivity of m-carboranylselenyl(II), -tellurenyl(II), and -tellurenyl(IV) chlorides and establish their reactivity pattern with Grignard reagents, alkenes, alkynes, enolates, and electron-rich arenes. These electrophilic reactions afford unique electron-rich B-Y-C (Y = Se, Te) bonding motifs not commonly found before. Furthermore, we show that m-carboranylselenolate, and even m-carboranyltellurolate, can be competent nucleophiles and participate in nucleophilic aromatic substitution reactions. Arene substitution chemistry is shown to be further extended to electron-rich species via palladium-mediated cross-coupling chemistry.
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Host-guest interactions represent a growing research area with recent work demonstrating the ability to chemically manipulate both host molecules as well as guest molecules to vary the type and strength of bonding. Much less is known about the interactions of the guest molecules and hybrid materials containing similar chemical features to typical macrocyclic hosts. This work uses in vitro and in vivo kinetic analyses to investigate the interaction of closo-dodecahydrododecaborate derivatives with ferumoxytol, an iron oxide nanoparticle with a carboxylated dextran coating. We find that several boron cluster derivatives can become encapsulated into ferumoxytol, and the lack of pH dependence in these interactions suggests that ion pairing, hydrophobic/hydrophilic interaction, and hydrogen bonding are not the driving force for encapsulation in this system. Biodistribution experiments in BALB/c mice show that this system is nontoxic at the reported dosage and demonstrate that encapsulation of dodecaborate-based clusters in ferumoxytol can alter the biodistribution of the guest molecules.