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Computational studies for a series of low to high strain anti-Bredt alkenes suggest that those with highly twisted bridgehead double bonds and a small singlet-triplet energy gap may undergo facile stepwise [2 + 2] cycloadditions to furnish four membered rings. A selection of reaction substrates, including ethylene, acetylene, perfluoroethylene, and cyclooctyne are considered.
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Pentalenes are formally eight-π-electron antiaromatic, but π-expanded pentalenes can display varying levels of paratropicity depending on the choice of annelated (hetero)arenes and the geometry of π-expansion (i.e., linear vs bent topologies) around the [4n] core. Here, we explain the effects of annelation on the paratropicity of π-expanded pentalenes by relating the electronic structure of pentalenes to a pair of conjoined pentafulvenes.
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The first tunable nano-bending structures of [1]rotaxane containing a single-fluorophoric N,N'-diphenyl-dihydrodibenzo[a,c]phenazine (DPAC) moiety (i.e., [1]RA) are developed as a loosened lasso structure to feature the bright white-light emission [CIE (0.27, 0.33), Φ = 21.2%] in THF solution, where bi-stable states of bending and twisted structures of DPAC unit in [1]RA produce cyan and orange emissions at 480 and 600 nm, respectively. With acid/base controls, tunable loosened/tightened nano-loops of corresponding [1]rotaxanes (i.e., [1]RA/[1]RB) can be achieved via the shuttling of macrocycles reversibly, and thus to adjust their respective white-light/cyan emissions, where the cyan emission of [1]RB is obtained due to the largest conformational constraint of DPAC moiety in its bending form of [1]RB with a tightened lasso structure. Additionally, the non-interlocked analog M-Boc only shows the orange emission, revealing the twisted form of DPAC fluorophore in M-Boc without any conformational constraint. Moreover, the utilization of solvents (with different viscosities and polarities), temperatures, and water fractions could serve as effective tools to adjust the bi-stable vibration-induced emission (VIE) colors of [1]rotaxanes. Finally, tuning ratiometric emission colors of adaptive conformations of DPAC moieties by altering nano-bending structures in [1]rotaxanes and external stimuli can be further developed as intelligent temperature and viscosity sensor materials.
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Whether tetra-tert-butyl-s-indacene is a symmetric D2h structure or a bond-alternating C2h structure remains a standing puzzle. Close agreement between experimental and computed proton chemical shifts based on minima structures optimized at the M06-2X, ωB97X-D, and M11 levels confirm a bond-localized C2h symmetry, which is consistent with the expected strong antiaromaticity of TtB-s-indacene.
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Aromaticity is one of the most deeply rooted concepts in chemistry. But why, if two-thirds of existing compounds can be classified as aromatic, is there no consensus on what aromaticity is? σ-, π-, δ-, spherical, Möbius, or all-metal aromaticity why are so many attributes needed to specify a property? Is aromaticity a dubious concept? This perspective aims to reflect where the aromaticity community is and where it is going.
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The lack of efficient and robust deep-blue phosphorescent metal complexes remains a significant challenge in the context of electroluminescent color displays. The emissive triplet states of blue phosphors are deactivated by low-lying metal-centered (3MC) states, which can be ameliorated by increasing the σ-donating ability of the supporting ligands. Here we unveil a synthetic strategy to access blue-phosphorescent complexes with two supporting acyclic diaminocarbenes (ADCs), known to be even stronger σ-donors than N-heterocyclic carbenes (NHCs). This new class of platinum complexes has excellent photoluminescence quantum yields, with four of six complexes affording deep-blue emission. Experimental and computational analyses are consistent with a pronounced destabilization of the 3MC states by the ADCs.
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Organic electrode materials could revolutionize batteries because of their high energy densities, the use of Earth-abundant elements, and structural diversity which allows fine-tuning of electrochemical properties. However, small organic molecules and intermediates formed during their redox cycling in lithium-ion batteries (LIBs) have high solubility in organic electrolytes, leading to rapid decay of cycling performance. We report the use of three cyclotetrabenzil octaketone macrocycles as cathode materials for LIBs. The rigid and insoluble naphthalene-based cyclotetrabenzil reversibly accepts eight electrons in a two-step process with a specific capacity of 279â mAh g-1 and a stable cycling performance with ≈65 % capacity retention after 135â cycles. DFT calculations indicate that its reduction increases both ring strain and ring rigidity, as demonstrated by computed high distortion energies, repulsive regions in NCI plots, and close [Câ â â C] contacts between the naphthalenes. This work highlights the importance of shape-persistency and ring strain in the design of redox-active macrocycles that maintain very low solubility in various redox states.
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Bistable [c2] daisy chain rotaxanes with respective extended and contracted forms of [c2]A and [c2]B containing a blue-emissive anthracene (AN) donor and orange-emissive indandione-carbazole (IC) acceptor were successfully synthesized via click reaction. Tunable-emission bistable [c2] daisy chain rotaxanes with fluorescence changes from blue to orange, including bright-white-light emissions, could be modulated by the aggregation-induced emission (AIE) characteristics and Förster resonance energy transfer (FRET) processes through altering water fractions and shuttling processes (i.e., acid/base controls). Accordingly, as a result of excellent fine-tuning AIE (at 60% water content of H2O/THF) and FRET (with a compatible energy transfer of EFRET = 33.2%) behaviors after the shuttling process (by adding base), the brightest white-light emission at CIE (0.31, 0.37) with a quantum yield of Φ = 15.64% was obtained in contracted [c2]B with good control of molecular shuttling to possess higher photoluminescence (PL) quantum yields and better energy transfer efficiencies (i.e., the manipulation of reduced PET and enhanced FRET processes) due to their intramolecular aggregations of blue AN donors and orange IC acceptors with a proper water content of 60% H2O. Furthermore, dynamic light-scattering (DLS) and time-resolved photoluminescence (TRPL) measurements, along with theoretical calculations, were utilized to investigate and confirm AIE and FRET phenomena of bistable [c2] daisy chain rotaxanes. Especially, both bistable [c2] daisy chain rotaxanes [c2]A and [c2]B and noninterlocked monomer M could be exploited for the applications of ratiometric fluorescence temperature sensing due to the temperature effects on the AIE and FRET features. Based on these desirable bistable [c2] daisy chain rotaxane structures, this work provides a potential strategy for the future applications of tunable multicolor emission and ratiometric fluorescence temperature-sensing materials.
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The phosphaquinolinone scaffold has been previously studied as a modular core for a variety of fluorescent species where use of substituent effects has focused on increasing or decreasing electron density in the core rings. We now report the synthesis and analysis of several pyridine-containing phosphaquinolinone species exhibiting notable linear conjugation from the aryl-substituent to electron-withdrawing pyridyl nitrogen. Varying the nature of the aryl substituent from electron-withdrawing to electron-donating leads to the generation of an internal charge-transfer (ICT) band in the absorbance spectrum, which becomes the dominant absorbance in terms of intensity in the most electron-rich -NMe2 example. This heterocycle exhibits improved photophysical properties compared to others in the set including high quantum yield and considerably red-shifted emission. The enhanced ICT can be observed in the X-ray data where a rare example of molecule co-planarity is observed. Computational data show increased localization of negative charge on the pyridyl nitrogen as the electron-donating character of the aryl-substituent increases.
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The self-trapping nano-loop structures of [1]rotaxanes exhibited multiple Förster resonance energy transfer (FRET) patterns via dual and sequential locking/unlocking of pH-gated and UV exposure processes. As a tightened and constrained nano-loop in the acidic condition, dithienylethene (DTE) unit was locked in the highly bending open form to forbid ring closure upon UV irradiation.
Asunto(s)
Transferencia Resonante de Energía de Fluorescencia , Rotaxanos , Rotaxanos/química , Rayos UltravioletaRESUMEN
Manipulations of singlet oxygen (1 O2 ) generations by the integration of both aggregation-induced emission luminogen (AIEgen) photosensitizer and photochromic moieties have diversified features in photodynamic therapy applications. Through Förster resonance energy transfer (FRET) pathway to induce red PL emissions (at 595 nm) for 1 O2 productions, [1]rotaxane containing photosensitive tetraphenylethylene (TPE) donor and photochromic diarylethene (DAE) acceptor is introduced to achieve dual and sequential locked/unlocked photoswitching effects by pH-controlled shuttling of its contracted/extended forms. Interestingly, the UV-enabled DAE ring closure speeds follow the reversed trend of DAE self-constraint degree as: contracted < extended < noninterlocked forms in [1]rotaxane analogues, thus FRET processes can be adjusted in contracted/extended forms of [1]rotaxane upon UV irradiations. Accordingly, the contracted form of [1]rotaxane is FRET-OFF locked and inert to UV exposure due to the larger bending conformation of DAE parallel (p-)conformer, compared with its extended and noninterlocked analogues possessing switchable FRET-OFF/ON behaviors activated by dual and sequential pH- and photoswitching. Owing to the advantages of 1 O2 productions tuned by multistimuli inputs (pH, UV, and blue light), an useful logic circuit for toxicity outputs of the surface modified [1]rotaxane nanoparticles (NPs) has been demonstrated to offer promising 1 O2 productions and managements based on mechanically interlocked molecules for future bioapplications.
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We introduce phosphorescent platinum aryl acetylide complexes supported by tert-butyl-isocyanide and strongly σ-donating acyclic diaminocarbene (ADC) ligands. The precursor complexes cis-[Pt(CNtBu)2(C≡CAr)2] (4a-4f) are treated with diethylamine, which undergoes nucleophilic addition with one of the isocyanides to form the cis-[Pt(CNtBu)(ADC)(C≡CAr)2] complexes (5a-5f). The new compounds incorporate either electron-donating groups (4-OMe and 4-NMe2) or electron-withdrawing groups [3,5-(OMe)2, 3,5-(CF3)2, 4-CN, and 4-NO2] on the aryl acetylide. Experimental HOMO-LUMO gaps, estimated from cyclic voltammetry, span the range of 2.68-3.61 eV and are in most cases smaller than the unsubstituted parent complex, as corroborated by DFT. In the ADC complexes, peak photoluminescence wavelengths span the range of 428 nm (2a, unsubstituted phenylacetylide) to 525 nm (5f, 4-NO2-substituted), with the substituents inducing a red shift in all cases. The phosphorescence E0,0 values and electrochemical HOMO-LUMO gaps are loosely correlated, showing that both can be reduced by either electron-donating or electron-withdrawing substituents on the aryl acetylides. The photoluminescence quantum yields in the ADC complexes are between 0.044 and 0.31 and the lifetimes are between 4.8 and 14 µs, a factor of 1.8-10× higher (for ΦPL) and 1.2-3.6× longer (for τ) than the respective isocyanide precursor (ΦPL = 0.014-0.12, τ = 2.8-8.2 µs).
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Inclusion of a second nitrogen atom in the aromatic core of phosphorus-nitrogen (PN) heterocycles results in unexpected tautomerization to a nonaromatic form. This tautomerization, initially observed in the solid state through X-ray crystallography, is also explained by computational analysis. We prepared an electron deficient analogue (2 e) with a fluorine on the pyridine ring and showed that the weakly basic pyridine resisted tautomerization, providing key insights to why the transformation occurs. To study the difference in solution vs. solid-state heterocycles, alkylated analogues that lock in the quinoidal tautomer were synthesized and their different 1 H NMR and UV/Vis spectra studied. Ultimately, we determined that all heterocycles are the aromatic tautomer in solution and all but 2 e switch to the quinoidal tautomer in the solid state. Better understanding of this transformation and under what circumstances it occurs suggest future use in a switchable on/off hydrogen-bond-directed receptor that can be tuned for complementary hydrogen bonding.
Asunto(s)
Nitrógeno , Fósforo , Enlace de Hidrógeno , PiridinasRESUMEN
Computed nucleus-independent chemical shifts (NICS), contour plots of isotropic magnetic shielding (IMS), and gauge-including magnetically induced current (GIMIC) plots suggest that polarization of the π-system of acridones may perturb the numbers and positions of Clar sextet rings. Decreasing numbers of Clar sextets are connected to experimental observations of a narrowing HOMO-LUMO gap and increased charge mobility in solid-state assemblies of quinacridone and epindolidione.
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Many popular organic chromophores that catalyze photoinduced proton-coupled electron transfer (PCET) reactions are aromatic in the ground state but become excited-state antiaromatic in the lowest ππ* state. We show that excited-state antiaromaticity makes electron transfer easier. Two representative photoinduced electron transfer processes are investigated: (1) the photolysis of phenol and (2) solar water splitting of a pyridine-water complex. In the selected reactions, the directions of electron transfer are opposite, but the net result is proton transfer following the direction of electron transfer. Nucleus-independent chemical shifts (NICS), ionization energies, electron affinities, and PCET energy profiles of selected [4n] and [4n + 2] π-systems are presented, and important mechanistic implications are discussed.
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Electrones , Fenol/química , Piridinas/química , Agua/química , Luz , Fenol/efectos de la radiación , Fotólisis , Piridinas/efectos de la radiación , Teoría CuánticaRESUMEN
We examine the effects of fusing two benzofurans to s-indacene (indacenodibenzofurans, IDBFs) and dicyclopenta[b,g]naphthalene (indenoindenodibenzofurans, IIDBFs) to control the strong antiaromaticity and diradical character of these core units. Synthesis via 3-functionalized benzofuran yields syn-IDBF and syn-IIDBF. syn-IDBF possesses a high degree of paratropicity, exceeding that of the parent hydrocarbon, which in turn results in strong diradical character for syn-IIDBF. In the case of the anti-isomers, synthesized via 2-substituted benzofurans, these effects are decreased; however, both derivatives undergo an unexpected ring-opening reaction during the final dearomatization step. All the results are compared to the benzothiophene-fused analogues and show that the increased electronegativity of oxygen in the syn-fused derivatives leads to enhancement of the antiaromatic core causing greater paratropicity. For syn-IIDBF increased diradical character results from rearomati-zation of the core naphthalene unit in order to relieve this paratropicity.
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The novel multistimuli-responsive monofluorophoric supramolecular polymer Poly(TPE-DBC)/FL-DBA and pseudo[3]rotaxane TPE-DBC/FL-DBA consisted of the closed form of nonemissive fluorescein guest FL-DBA along with TPE-based main-chain macrocyclic polymer Poly(TPE-DBC) and TPE-functionalized macrocycle TPE-DBC hosts, respectively. By the combination of various external stimuli, these fluorescent supramolecular host-guest systems could reveal interesting photoluminescence (PL) properties in DMF/H2O (1:1, v/v) solutions, including bifluorophoric host-guest systems after the complexation of Al3+ ion, i.e., TPE-DBC/FL-DBA-Al3+ and Poly(TPE-DBC)/FL-DBA-Al3+ with their corresponding open form of fluorescein guest FL-DBA-Al3+. Importantly, the Förster resonance energy transfer (FRET) processes occurred in both bifluorophoric host-guest systems between blue-emissive TPE donors (λem = 470 nm) and green-emissive fluorescein acceptors (λem = 527 nm) after aluminum detection, which were further verified by time-resolved photoluminescence (TRPL) measurements to acquire their FRET efficiencies of 40.4 and 31.1%, respectively. Both supramolecular host-guest systems exhibited stronger green fluorescein emissions as well as appealing ratiometric PL behaviors within the desirable donor-acceptor distances of FRET processes in comparison with their detached analogous mixtures. Regarding the pH effects, the optimum green fluorescein emissions with effective FRET processes of all compounds and host-guest systems were sustained in the range pH = 7-10. Interestingly, both host-guest systems TPE-DBC/FL-DBA and Poly(TPE-DBC)/FL-DBA possessed high sensitivities and selectivities toward aluminum ion to display their strong green emissions via FRET-ON behaviors due to the chelation-induced ring opening of spirolactam moieties to become green-emissive guest acceptor FL-DBA-Al3+, which offered excellent limit of detection (LOD) values of 50.61 and 38.59 nM, respectively, to be further applied for the fabrication of facile test strips toward aluminum detection. Accordingly, the inventive ratiometric PL and FRET sensor approaches of supramolecular host-guest systems toward aluminum ion with prominent sensitivities and selectivities were well-established in this study.
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In this paper, we report a series of six neutral, blue-phosphorescent cyclometalated iridium complexes of the type Ir(C^Y)2(CNAr)(CN). The cyclometalating ligands in these compounds (C^Y) are either aryl-substituted 1,2,4-triazole or NHC ligands, known to produce complexes with blue phosphorescence. These cyclometalating ligands are paired with π-acidic, strongly σ-donating cyano and aryl isocyanide (CNAr) ancillary ligands, the hypothesis being that these ancillary ligands would destabilize the higher-lying ligand-field (d-d) excited states, allowing efficient blue photoluminescence. The compounds are prepared by substituting the cyanide ancillary ligand onto a chloride precursor and are characterized by NMR, mass spectrometry, infrared spectroscopy, and, for five of the compounds, by X-ray crystallography. Cyclic voltammetry establishes that these compounds have large HOMO-LUMO gaps. The mixed cyano-isocyanide compounds are weakly luminescent in solution, but they phosphoresce with moderate to good efficiency when doped into poly(methyl methacrylate) films, with Commission Internationale de L'Eclairage coordinates that indicate deep blue emission for five of the six compounds. The photophysical studies show that the photoluminescence quantum yields are greatly enhanced in the cyano complexes relative to the chloride precursors, affirming the benefit of strong-field ancillary ligands in the design of blue-phosphorescent complexes. Density functional theory calculations confirm that this enhancement arises from a significant destabilization of the higher-energy ligand-field states in the cyanide complexes relative to the chloride precursors.