RESUMO
Highly reactive arylalkylcarbenes generated in solution by photolysis of their aryldiazoalkane precursors tend to undergo competing inter- and intramolecular reactions to yield a complex mixture of products. Having previously shown the use of crystals to effectively control the reactivity of arylalkylcarbenes to afford high yields of a single product, it was of interest to investigate whether the crystalline environment could also enable spectroscopic detection of these intermediates en route to the photoproduct. Using 1,2,2-triphenyldiazoethane (3) as a model substrate to probe the effect of alternative reaction trajectories that yield triphenylethylene (5) by competing 1,2-H shift or 1,2-Ph migration, we report selectivities consistent with reaction from a spin-equilibrated carbene 4 in solution, while reactions in crystals primarily afford alkene 5 via a lattice-controlled 1,2-H shift. Attempts to detect 1,2,2-triphenylethylidene 4 in crystals by nanosecond laser-flash photolysis or by triplet-triplet fluorescence at 77 K were unsuccessful, indicating that arylalkylcarbenes possessing α-H substituents undergo facile 1,2-H shifts both in solution and in the solid state. However, related tert-butylphenylmethylene with no α-H substituents could be observed by triplet-triplet fluorescence at 77 K in glassy matrices.
RESUMO
Photochemical valence bond isomerization of a crystalline Dewar benzene (DB) diacid monoanion salt with an acetophenone-linked piperazinium cation that serves as an intramolecular triplet energy sensitizer (DB-AcPh-Pz) exhibits a quantum chain reaction with as many as 450 product molecules per photon absorbed (Φ ≈ 450). By contrast, isomorphous crystals of the DB diacid monosalt of an ethylbenzene-linked piperazinium (DB-EtPh-Pz) lacking a triplet sensitizer showed a less impressive quantum yield of ca. Φ ≈ 22. To establish the critical importance of a triplet excited state carrier in the adiabatic photochemical reaction we prepared mixed crystals with DB-AcPh-Pz as a dilute triplet sensitizer guest in crystals of DB-EtPh-Pz. As expected from their high structural similarities, solid solutions were easily formed with the triplet sensitizer salt in the range of 0.1 to 10%. Experiments carried out under conditions where light is absorbed by the triplet sensitizer-linked DB-AcPh-Pz can be used to initiate a triplet state adiabatic reaction from 3DB-AcPh-Pz to 3HB*-AcPh-Pz, which can serve as a chain carrier and transfer energy to an unreacted DB-EtPh-Pz where exciton delocalization in the crystalline solid solution can help carry out an efficient energy transfer and enable a quantum chain employing the photoproduct as a triplet chain carrier. Excitation of mixed crystals with as little as 0.1% triplet sensitizer resulted in an extraordinarily high quantum yield Φ ≈ 517.
RESUMO
Ground-state destabilization is a promising strategy to modulate rotational barriers in amphidynamic crystals. Density functional theory studies of polar phenylenes installed as rotators in pillared paddle-wheel metal organic frameworks were performed to investigate the effects of ground-state destabilization on their rotational dynamics. We found that as the steric size of phenylene substituents increases, the ground-state destabilization effect is also increased. Specifically, a significant destabilization of the ground-state energy occurred as the size of the substituents increased, with values ranging from 2 to 11.7 kcal/mol. An evaluation of the effects of substituents on dipole-dipole interaction energies and rotational barriers suggests that it should be possible to engineer amphidynamic crystals where the dipole-dipole interaction energy becomes comparable to the rotational barriers. Notably, while pure dipole-dipole interaction energies reached values ranging from 0.6 to 2.4 kcal/mol, the inclusion of electronic and steric effects can alter dipolar orientations to significantly greater values. We propose that careful selection of polar substituents with different sizes may help create temperature-responsive materials with switchable collective polarization.
RESUMO
Crystals of 4,4'-dimethylbenzophenone (DMBP) are known to react by intermolecular H atom transfer, followed by radical pair recombination. To determine the contribution of the H atom transfer reaction to the deactivation of the triplet ketone, transient absorption spectra and kinetics were obtained using aqueous nanocrystalline suspensions. Single-exponential lifetimes of ca. 1185 ns with no deuterium isotope effect and inefficient product formation suggest that the reaction does not contribute significantly to the kinetics of triplet decay. By contrast, the observed lifetime is consistent with previous observations with p,p'-disubstituted benzophenones that undergo an efficient self-quenching process by a reductive charge transfer mechanism.
RESUMO
Quantum chain reactions are characterized by the formation of several photoproducts per photon absorbed (ΦQC > 1) and constitute a promising signal amplification mechanism. The triplet-sensitized isomerization of Dewar benzene is known to undergo quantum chain reactions characterized by an adiabatic valence-bond isomerization to the excited state of Hückel benzene, which is able to transfer its triplet energy to a new ground state Dewar benzene that reacts to continue the chain. Given that diffusion-mediated energy transfer is the chain-limiting event in solution, we demonstrate here that reactions in crystals are significantly more efficient by taking advantage of energy transfer by a presumed exciton delocalization mechanism. Using Dewar benzenes with covalently attached, high energy triplet sensitizers we have demonstrated the efficiency of the solid state by the amplification of a quantum yield of ca. ΦQC ≈ 76 in acetonitrile solution to as much as ca. ΦQC ≈ 100-120 in submicron size specimens prepared by the re-precipitation method, and up to ca. ΦQC ≈ 300 with microcrystalline powders suspended in water.
RESUMO
Triplet acyl-alkyl radical pairs generated by pulsed laser excitation within the constraints of their nanocrystalline ketone precursors were recently introduced as a potential platform for the robust and repeated instantiation of spin qubit pairs for applications in quantum information science. Here, we report the transient spectroscopy of a series of nanocrystalline trityl-alkyl and trityl-aryl ketones capable of generating correlated triplet radical pairs with persistent triphenylmethyl radicals forced to remain within bonding distances of highly reactive acyl radicals. Whereas triplet trityl-acyl radical pairs decay by competing product-forming decarbonylation and intersystem crossing, triplet trityl-benzoyl radical pairs have lifetimes of up to ca. 4 ms and exclusively regenerate the starting ketone. We propose that these long lifetimes are the result of the short inter-radical distances and the colinear orientation of the two singly occupied orbitals, which are expected to result in large singlet-triplet energy gaps, large zero-field splitting parameters, and a poor geometry for spin-obit coupling. Ketones generating trityl-benzoyl radical pairs demonstrate promising performance along multiple dimensions that are crucial for quantum information science.
Assuntos
Cetonas , Luz , Espectroscopia de Ressonância de Spin EletrônicaRESUMO
The cyclopropane ring features prominently in active pharmaceuticals, and this has spurred the development of synthetic methodologies that effectively incorporate this highly strained motif into such molecules. As such, elegant solutions to prepare densely functionalized cyclopropanes, particularly ones embedded within the core of complex structures, have become increasingly sought-after. Here we report the stereospecific synthesis of a set of cyclopropanes with vicinal quaternary stereocenters via the solvent-free solid-state photodenitrogenation of crystalline 1-pyrazolines. Density functional theory calculations at the M062X/6-31+G(d,p) level of theory were used to determine the origin of regioselectivity for the synthesis of the 1-pyrazolines; favorable in-phase frontier molecular orbital interactions are responsible for the observation of a single pyrazoline regioisomer. It was also shown that the loss of N2 may take place via a highly selective solid-state thermal reaction. Scalability of the solid-state photoreaction is enabled through aqueous nanocrystalline suspensions, making this method a "greener" alternative to effectively facilitate the construction of cyclopropane-containing molecular scaffolds.
Assuntos
Ciclopropanos , Ciclopropanos/químicaRESUMO
Artificial molecular machines are expected to operate in environments where viscous forces impact molecules significantly. With that, it is well-known that solvent behaviors dramatically change upon confinement into limited spaces as compared to bulk solvents. In this study, we demonstrate the utility of an amphidynamic metal-organic framework with pillars consisting of 2H-labeled dialkynyltriptycene and dialkynylphenylene barrierless rotators that operate as NMR sensors for solvent viscosity. Using line-shape analysis of quadrupolar spin echo spectra we showed that solvents such as dimethylformamide, diethylformamide, 2-octanone, bromobenzene, o-dichlorobenzene, and benzonitrile slow down their Brownian rotational motion (103-106 s-1) to values consistent with confined viscosity values (ca. 100-103 pa s) that are up to 10000 greater than those in the bulk. Magic angle spinning assisted 1H T2 measurements of included solvents revealed relaxation times of approximately 100-1000 ms over the explored temperature ranges, and MAS-assisted 1H T1 measurements of included solvents suggested a much lower activation energy for rotational dynamics as compared to those measured by the rotating pillars using 2H measurements. Finally, translational diffusion measurements of DMF using pulsed-field gradient methods revealed intermediate dynamics for the translational motion of the solvent molecules in MOFs.
RESUMO
Radical pairs generated in crystalline solids by bond cleavage reactions of triplet ketones offer the unique opportunity to explore a frontier of spin dynamics where rigid radicals are highly entangled as the result of short inter-radical distances, large singlet-triplet energy gaps (ΔEST), and limited spin-lattice relaxation mechanisms. Here we report the pulsed laser generation and detection of strongly entangled triplet acyl-alkyl radical pairs generated in nanocrystalline suspensions of 1,1-diphenylmethyl 2-ketones with various 3-admantyl substituents. The sought-after triplet acyl-alkyl radical pairs could be studied for the first time in the solid state by taking advantage of the efficient triplet excited state α-cleavage reactions of 1,1-diphenylmethyl ketones and the slow rate of CO loss from the acyl radicals, which would have to generate highly unstable phenyl and primary alkyl radicals or relatively unstable secondary and tertiary alkyl radicals. With the loss of CO prevented, the lifetime of the triplet acyl-alkyl radical pair intermediates is determined by intersystem crossing to the singlet radical pair state, which is followed by immediate bond formation to the ground state starting ketone. Experimental results revealed biexponential kinetics with long-lived components that account for ca. 87-92% of the transient population and lifetimes that extend to the range of 53-63 µs, the longest reported so far for this type of radical pair. Structural information inferred from the starting ketone will make it possible to analyze the affects of proximity and orientation of the singly occupied orbitals and potentially help set a path for the use of triplet radical pairs as qubits in quantum information technologies.
RESUMO
A zirconium metal-organic framework with a difluorophenylene rotator bearing a permanent electric dipole of â¼3.2 D was synthesized, and its rotational motion was analyzed by temperature- and frequency-dependent broadband dielectric spectroscopy. While solid-state NMR confirms fast rotation qualitatively, the dissipation factors measured between 113 and 153 K suggested an activation energy Ea = 2.6 kcal/mol, but deviations from a single Debye relaxation suggested a dynamic process that cannot be accounted for by a well-defined potential with a single activation barrier. The dynamic heterogeneity of the dipolar rotor was confirmed by analysis in terms of a Cole-Cole relaxation, which suggested a mean barrier of â¼1.9 kcal/mol, with a heterogeneity that decreases as temperature increases. Based on the single-crystal structure, we propose that the kinetic heterogeneity results from a temperature-dependent potential where rotation motion is mediated by the escape of the rotator from an energy well created by a double Ph-H···F-Ph hydrogen bond.
RESUMO
Molecular spur gear dynamics with high gearing fidelity can be achieved through a careful selection of constituent molecular components that favorably position and maintain the two gears in a meshed configuration. Here, we report the synthesis of a new macrocyclic molecular spur gear with a bibenzimidazole stator combined with a second naphthyl bis-gold-phosphine gold complex stator to place two 3-fold symmetric 9,10-diethynyl triptycene cogs at the optimal distance of 8.1 Å for gearing. Micro electron diffraction (µED) analysis confirmed the formation of the macrocyclic structure and the proper alignment of the triptycene cogs. Gearing dynamics in solution are predicted to be extremely fast and, in fact, were too fast to be observed with variable-temperature 1H NMR using CD2Cl2 as the solvent. A combination of molecular dynamics and metadynamics simulations predict that the barriers for gearing and slippage are ca. 4 kcal mol-1 and ca. 9 kcal mol-1, respectively. This system is characterized by enhanced gearing fidelity compared to the acyclic analog. This is achieved by rigidification of the structure, locking the two triptycenes in the preferred gearing distance and orientation.
RESUMO
Solid-state photodecarbonylation is an attractive but underutilized methodology to forge hindered C-C bonds in complex molecules. This study discloses the use of this reaction to assemble the vicinal quaternary stereocenter motif present in bis(cyclotryptamine) alkaloids. Our strategy was enabled by experimental and computational investigations of the role of substrate conformation on the success or failure of the solid-state photodecarbonylation reaction. This informed a crystal engineering strategy to optimize the key step of the total synthesis. Ultimately, this endeavor culminated in the successful synthesis of the bis(cyclotryptamine) alkaloid "psychotriadine," which features the elusive piperidinoindoline framework. Psychotriadine, a previously unknown compound, was identified in the extracts of the flower Psychotria colorata, suggesting it is a naturally occurring metabolite.
Assuntos
Alcaloides/síntese química , Alcaloides/química , Carbono/química , Radicais Livres/química , Indóis/química , Luz , Conformação Molecular , Piperidinas/química , EstereoisomerismoRESUMO
In crystalline solids, molecules generally have limited mobility due to their densely packed environment. However, structural information at the molecular level may be used to design amphidynamic crystals with rotating elements linked to rigid, lattice-forming parts, which may lead to molecular rotary motions and changes in conformation that determine the physical properties of the solid-state materials. Here, we report a novel design of emissive crystalline molecular rotors with a central pyrazine rotator connected by implanted transition metals (Cu or Au) to a readily accessible enclosure formed by two N-heterocyclic carbenes (NHC) in discrete binuclear complexes. The activation energies for the rotation could be tuned by changing the implanted metal. Exchanging Cu to Au resulted in an â¼4.0 kcal/mol reduction in the rotational energy barrier as a result of lower steric demand by elongation of the axle with the noble metal, and a stronger electronic stabilization in the rotational transition state by enhancement of the d-π* interactions between the metal centers and the pyrazine rotator. The Cu(I) rotor complex showed a greater electronic delocalization than the Au(I) rotor complex, causing a red-shifted solid-state emission. Molecular rotation-induced emission quenching was observed in both crystals. The enclosing NHC rotors are easy to prepare, and their rotational motion should be less dependent on packing structures, which are often crucial for many previously documented amphidynamic molecular crystals. The platform from the encapsulating NHC cationic metal complexes and the metal-centered rotation-axis provide a promising scaffold for a novel design of crystalline molecular rotors, including manipulation of rotary dynamics and solid-state emission.
RESUMO
We report the synthesis and stereospecific solid-state photodecarbonylation of a hexasubstituted ketone featuring six distinct α-substituents. The photoproduct of the solid-state transformation features vicinal all-carbon quaternary stereocenters. While reactions carried out in bulk powders and aqueous crystalline suspensions were complicated by secondary photochemistry of the primary photoproduct, optimal conditions provided good yields and recyclable starting material. Subsequent transformations of the α-substituents having orthogonal chemical reactivity illustrate the potential of this transformation toward constructing complex architectures.
RESUMO
The creation of ordered arrays of qubits that can be interfaced from the macroscopic world is an essential challenge for the development of quantum information science (QIS) currently being explored by chemists and physicists. Recently, porous metal-organic frameworks (MOFs) have arisen as a promising solution to this challenge as they allow for atomic-level spatial control of the molecular subunits that comprise their structures. To date, no organic qubit candidates have been installed in MOFs despite their structural variability and promise for creating systems with adjustable properties. With this in mind, we report the development of a pillared-paddlewheel-type MOF structure that contains 4,7-bis(2-(4-pyridyl)-ethynyl) isoindoline N-oxide and 1,4-bis(2-(4-pyridyl)-ethynyl)-benzene pillars that connect 2D sheets of 9,10-dicarboxytriptycene struts and Zn2(CO2)4 secondary binding units. The design allows for the formation of ordered arrays of reorienting isoindoline nitroxide spin centers with variable concentrations through the use of mixed crystals containing the secondary 1,4-phenylene pillar. While solvent removal causes decomposition of the MOF, magnetometry measurements of the MOF containing only N-oxide pillars demonstrated magnetic interactions with changes in magnetic moment as a function of temperature between 150 and 5 K. Variable-temperature electron paramagnetic resonance (EPR) experiments show that the nitroxides couple to one another at distances as long as 2 nm, but act independently at distances of 10 nm or more. We also use a specially designed resonance microwave cavity to measure the face-dependent EPR spectra of the crystal, demonstrating that it has anisotropic interactions with impingent electromagnetic radiation.
RESUMO
The rotational dynamics of dirhodium supramolecular gears, formed with four 9-triptycene carboxylates cyclically arranged around a dirhodium core with variable axial ligands as originally designed by Shionoya et al., provide an excellent opportunity to evaluate the potential of computational methods and expand our understanding of the factors determining geared dynamics. Rotational dynamic rates in these structures depend on the nature of the axial ligand as shown by simulations over timescales that are not accessible experimentally. Molecular dynamics simulations gave information on the gearing mechanism, and the activation barriers to gearing were calculated using density functional theory. Steric demands imposed by the axial ligand were quantified using buried volume analysis. We found that gearing takes place in all six dirhodium-gear complexes with different axial ligands and that rotational barriers depend on their steric size.
RESUMO
Bis(cyclotryptamine) alkaloids have been popular topics of study for many decades. Five possible scaffolds for bis(cyclotryptamine) alkaloids were originally postulated in the 1950s, but only four of these scaffolds have been observed in natural products to date. We describe synthetic access to the elusive fifth scaffold, the piperidinoindoline, through syntheses of compounds now termed "dihydropsychotriadine" and "psychotriadine". The latter of these compounds was subsequently identified in extracts of the flower Psychotria colorata. Our synthetic route features a stereospecific solid-state photodecarbonylation reaction to introduce the key vicinal quaternary stereocenters.
Assuntos
Alcaloides/síntese química , Produtos Biológicos/síntese química , Indóis/química , Piperidinas/química , Triptaminas/síntese química , Alcaloides/química , Produtos Biológicos/química , Flores/química , Estrutura Molecular , Psychotria/química , Estereoisomerismo , Triptaminas/químicaRESUMO
Herein, we report the use of fluorescence anisotropy decay for measuring the rotation of six shape-persistent molecular rotors with central naphthalene (2), anthracene (3a, 3b, and 3c), tetracene (4), and pentacene (5) rotators axially linked by triple bonds to bulky trialkylsilyl groups of different sizes. Steady-state and time-resolved polarization measurements carried out in mineral oil confirmed that the vibrationally resolved lowest-energy absorption bands are characterized by a transition dipole moment oriented along the short acene axes, in the direction of the alkyne linkers. Fluorescence lifetimes increased significantly with increasing acene size and moderately with a decrease in the size of the trialkylsilyl group. The fluorescence anisotropy decay for all compounds in mineral oil with a viscosity of ca. 21.6 cP at 40 °C was completed within the fluorescence lifetime, so that the rotational time constants could be obtained via their rotational correlation times, which increased with silyl protecting group size rather than acene size, indicating that polarization decay is determined by tumbling of the molecular rotor about the long acene axis. These results suggest that monitoring the rotational motion of bis(silylethynyl)acenes in restricted media should be possible for media with viscosity values on the order of 21.6 cP or greater.
RESUMO
The synthesis of conjugated Möbius molecules remains elusive since twisted and macrocyclic structures are low-entropy species sporting their own synthetic challenges. Here we report the synthesis of a Möbius macrocycle in 84% yield via alkyne metathesis of 2,13-bis(propynyl)[5]helicene. MALDI-MS, NMR spectroscopy, and X-ray diffraction indicated a trimeric product of twofold symmetry with PPM/MMP configurations in the helicene subunits. Alternatively, a threefold-symmetric PPP/MMM structure was determined by DFT calculations to be more thermodynamically stable, illustrating remarkable kinetic selectivity for this alkyne metathesis cyclooligomerization. Computational studies provided insight into the kinetic selectivity, demonstrating a difference of 15.4 kcal/mol between the activation barriers for the PPM/MMP and PPP/MMM diastereodetermining steps. Computational (ACID and EDDB) and experimental (UV-vis and fluorescence spectroscopy and cyclic voltammetry) studies revealed weak conjugation between the alkyne and adjacent helicene groups as well as the lack of significant global aromaticity. Separation of the PPM and MMP enantiomers was achieved via chiral HPLC at the analytical scale.
RESUMO
We report synthetic efforts toward the regiocontrolled installation of the prenyl moiety in debromoflustramine A by the regiospecific photodecarbonylation of a prenyl-substituted ketone. Synthetic approaches to access the plausible photodecarbonylation substrates beginning from tryptamine were evaluated. Initial attempts to synthesize a suitable substrate for photodecarbonylation were hampered by a lack of substrate crystallinity (a prerequisite for solid-state photochemistry). Ultimately, a crystalline substrate could be accessed to attempt the key step by judicious selection of N-substituents. Although the photodecarbonylation did not result in the desired reverse prenylation, this study highlights the troubleshooting and optimization required for crystal phase photochemistry and underscores methods that can be used to control substrate crystallinity.