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Loops are prevalent topological structures in cross-linked polymer networks, resulting from the folding of polymer chains back onto themselves. Traditionally, they have been considered as defects that compromise the mechanical properties of the network, leading to extensive efforts in synthesis to prevent their formation. In this study, we introduce the inclusion of cyclic dibenzo-24-crown-8 (DB24C8) moieties within the polymer network strands to form CCNs, and surprisingly, these loops enhance the mechanical performances of the network, leading to tough elastomers. The toughening effect can be attributed to the unique cyclic structure of DB24C8. The relatively small size and the presence of rigid phenyl rings provide the loops with relatively stable conformations, allowing for substantial energy dissipation upon the application of force. Furthermore, the DB24C8 rings possess a broad range of potential conformations, imparting the materials with exceptional elasticity. The synergistic combination of these two features effectively toughens the materials, resulting in a remarkable 66-fold increase in toughness compared to the control sample of covalent networks. Moreover, the mechanical properties, particularly the recovery performance of the network, can be effectively tuned by introducing guests to bind with DB24C8, such as potassium ions and secondary ammonium salts.
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The structures and bonding properties of several lithium polysulfide clusters LiSn-/0 (n = 3-5) and Li2S4-/0 were investigated by size-selected anion photoelectron spectroscopy coupled with quantum chemistry calculations. The vertical detachment energies of LiS3-, LiS4-, and LiS5- were estimated to be 2.17 ± 0.08, 3.30 ± 0.08 and 3.66 ± 0.08 eV, respectively, and that of Li2S4- was estimated to be 3.21 ± 0.08 eV. It is found that LiS3- and LiS3 have planar quadrilateral structures, and LiS4- and LiS4 have distorted five-membered ring structures. LiS5- has a distorted six-membered ring structure while neutral LiS5 has a book-shaped structure. The lowest-lying structure of Li2S4- can be viewed as a S2 unit connecting to the Li-Li edge of a Li2S2 tetrahedron. The lowest-lying structure of neutral Li2S4 can be viewed as a S2 unit connecting to the S atoms of a Li2S2 quadrilateral. The natural population analysis (NPA) and electron localization function (ELF) analyses show that the excess electron of LiSn- is mainly localized over the sulfur chains, especially on the S atoms interacting with Li, thus, the most stable structures of LiSn- can be regarded as a Li+ cation interacting with a Sn2- dianion. The results may be useful for understanding the formation of lithium polysulfides in lithium sulfur batteries.
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The structures of magnesium chloride dimer-water clusters, (MgCl2)2(H2O)n-/0, were investigated with size-selected anion photoelectron spectroscopy and theoretical calculations to understand the dissolution of magnesium chloride in water. The most stable structures were confirmed by comparing vertical detachment energies (VDEs) with the experimental measurements. A dramatic drop of VDE at n = 3 has been observed in the experiment, which is in accordance with the structural change of (MgCl2)2(H2O)n-. Compared to the neutral clusters, the excess electron induces two significant phenomena in (MgCl2)2(H2O)n-. First, the planar D2h geometry can be converted into a C3v structure at n = 0, making the Mg-Cl bonds easier to be broken by water molecules. More importantly, a negative charge-transfer-to-solvent process occurs after adding three water molecules (i.e., at n = 3), which leads to an obvious deviation in the evolution of the clusters. Such electron transfer behavior was noticed at n = 1 in monomer MgCl2(H2O)n-, indicating that the dimerization between two MgCl2 molecules can make the cluster more capable of binding electron. In neutral (MgCl2)2(H2O)n, this dimerization provides more sites for the added water molecules, which can stabilize the entire cluster and maintain its initial structure. Specifically, filling the coordination number to be 6 for Mg atoms can be seen as a link between structural preferences in the dissolution of the monomers, dimers, and extended bulk-state of MgCl2. This work represents an important step forward into fully understanding the solvation of MgCl2 crystals and other multivalent salt oligomers.
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The conformations of 1,7DSU and its stepwise solvation by up to 5 water molecules were explored using supersonic-jet Fourier transform microwave spectroscopy with the supplement of theoretical calculations. Experimentally, the rotational spectra of the most stable structures of the monomer, monohydrate and dihydrate were observed and assigned. The characteristics of the stability and intermolecular interaction topologies of the 1,7DSU monomer and its hydrated clusters were obtained by CREST conformational sampling followed by B3LYP-D3(BJ)/def2-TZVP geometrical optimizations and MP2/aug-cc-pVTZ single-point energy calculations. The first water molecule links to the 1,7DSU monomer through an OwHâ¯O hydrogen bond. The water molecules tend to aggregate with each other and form cyclic structures for the n = 2-5 clusters. The interactions between water and the 1,7DSU monomer as well as those between water and water were revealed. The analyses of non-covalent interactions and the natural bond orbital suggest that the OwHâ¯O1,7DSU, OwHâ¯Ow, and CHâ¯Ow hydrogen bonds play a prominent role in structural stability.
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To understand the microsolvation of alkaline-earth dihalides in water and provide information about the dependence of solvation processes on different halides, we investigated CaBr2(H2O)n-, CaI2(H2O)n-, and CaF2(H2O)n- (n = 0-6) clusters using size-selected anion photoelectron spectroscopy and conducted theoretical calculations on these clusters and their neutrals. The results are compared with those of CaCl2(H2O)n-/0 clusters reported previously. It is found that the vertical detachment energies (VDEs) of CaCl2(H2O)n-, CaBr2(H2O)n-, and CaI2(H2O)n- show a similar trend with increasing cluster size, while the VDEs of CaF2(H2O)n- show a different trend. The VDEs of CaF2(H2O)n- are much lower than those of CaCl2(H2O)n-, CaBr2(H2O)n-, and CaI2(H2O)n-. A detailed probing of the structures shows that a significant increase of the Ca-X distance (separation of Ca2+-X- ion pair) in CaCl2(H2O)n-/0, CaBr2(H2O)n-/0, and CaI2(H2O)n-/0 clusters occurred at about n = 5. However, for CaF2(H2O)n-/0, no abrupt change of the Ca-F distance with the increasing cluster size has been observed. In CaCl2(H2O)6-/0, CaBr2(H2O)6-/0, and CaI2(H2O)6-/0, the Ca atom coordinates directly with 5 H2O molecules. However, in CaF2(H2O)n-/0, the Ca atom coordinates directly with only 2 or 3 H2O molecules. The similarity or differences in the structures and coordination numbers are consistent with the fact that CaCl2, CaBr2, and CaI2 have similar solubility, while CaF2 has much lower solubility.
RESUMO
We studied (NaSCN)2(H2O)n - clusters in the gas phase using size-selected anion photoelectron spectroscopy. The photoelectron spectra and vertical detachment energies of (NaSCN)2(H2O)n - (n = 0-5) were obtained in the experiment. The structures of (NaSCN)2(H2O)n -/0 up to n = 7 were investigated with density functional theory calculations. Two series of peaks are observed in the spectra, indicating that two types of structures coexist, the high electron binding energy peaks correspond to the chain style structures, and the low electron binding energy peaks correspond to the Na-N-Na-N rhombic structures or their derivatives. For the (NaSCN)2(H2O)n - clusters at n = 3-5, the Na-N-Na-N rhombic structures are the dominant structures, the rhombic four-membered rings start to open at n = 4, and the solvent separated ion pair (SSIP) type of structures start to appear at n = 6. For the neutral (NaSCN)2(H2O)n clusters, the Na-N-Na-N rhombic isomers become the dominant starting at n = 3, and the SSIP type of structures start to appear at n = 5 and become dominant at n = 6. The structural evolution of (NaSCN)2(H2O)n -/0 (n = 0-7) confirms the possible existence of ionic clusters such as Na(SCN)2 - and Na2(SCN)+ in NaSCN aqueous solutions.
RESUMO
We studied NaSCN(H2O)n- clusters in the gas phase using size-selected anion photoelectron spectroscopy. Vertical detachment energies (VDEs) of NaSCN(H2O)n- (n = 0-6) clusters were obtained in the experiment. Structures of NaSCN(H2O)n- (n = 0-6) clusters and their corresponding neutral counterparts were investigated by theoretical calculations. Our studies show that the Na-NCS type of structures rather than the Na-SCN type of structures are dominant in the gas phase for both anionic and neutral NaSCN(H2O)n clusters. For NaSCN(H2O)n- anions, the contact ion pair (CIP) and solvent-separated ion pair (SSIP) type of structures coexist at n = 2 and 3, the SSIP type of structures become dominant at n ≥ 4. For neutral NaSCN(H2O)n, the CIP type of structures are dominant from n = 1 to 6 and the SSIP type of structures start to appear at n = 6. The gas phase structures in this work support the existence of ion clustering in concentrated NaSCN aqueous solutions.
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In order to understand the hydration processes of BaCl2, we investigated BaCl2(H2O)n - (n = 0-5) clusters using size-selected anion photoelectron spectroscopy and theoretical calculations. The structures of neutral BaCl2(H2O)n clusters up to n = 8 were also investigated by theoretical calculations. It is found that in BaCl2(H2O)n -/0, the Ba-Cl distances increase very slowly with the cluster size. The hydration process is not able to induce the breaking of a Ba-Cl bond in the cluster size range (n = 0-8) studied in this work. In small BaCl2(H2O)n clusters with n ≤ 5, the Ba atom has a coordination number of n + 2; however, in BaCl2(H2O)6-8 clusters, the Ba atom coordinates with two Cl atoms and (n - 1) water molecules, and it has a coordination number of n + 1. Unlike the previously studied MgCl2(H2O)n - and CaCl2(H2O)n -, negative charge-transfer-to-solvent behavior has not been observed for BaCl2(H2O)n -, and the excess electron of BaCl2(H2O)n - is mainly localized on the Ba atom rather on the water molecules. No observation of Ba2+-Cl- separation in current work is consistent with the lower solubility of BaCl2 compared to MgCl2 and CaCl2. Considering the BaCl2/H2O mole ratio in the saturated solution, one would expect that about 20-30 H2O molecules are needed to break the first Ba-Cl bond in BaCl2.
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Thermally activated delayed-fluorescent (TADF) materials are anticipated to overcome triplet-related losses towards electrically driven organic lasers. Thus far, contributions from triplets to lasing have not yet been experimentally demonstrated owing to the limited knowledge about the excited-state processes. Herein, we experimentally achieve reverse intersystem crossing (RISC)-boosted lasing in organic microspheres with uniformly dispersed TADF emitters. In these materials, triplets are continuously converted to radiative singlets through RISC, giving rise to reduced losses in stimulated emission. The involvement of regenerated singlets in population inversion results in a thermally activated lasing; that is, the lasing intensity increases with increasing temperature, accompanied by accelerated depletion of the excited-state population. Benefiting from the suppression of triplet accumulations by RISC processes, a high-repetition-rate microlaser was achieved.
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The structural and electronic properties of Cu3O3- and Cu3O4- were investigated using mass-selected anion photoelectron spectroscopy in combination with density functional theoretical calculations. The vertical detachment energies of Cu3O3- and Cu3O4- were measured to be 3.48 ± 0.08 and 3.54 ± 0.08 eV, respectively. Their geometrical structures were determined by comparison of the theoretical calculations with the experimental results. The most stable structure of Cu3O3- can be characterized as a C3v symmetric six-membered ring structure with alternating Cu-O bonds, in which the plane of the three O atoms is slightly above that of the three Cu atoms. The most stable structure of Cu3O4- can be viewed as a Cs symmetric seven-membered ring with a peroxo unit. The bond order and molecular orbital analyses indicate that the Cu-Cu interactions in Cu3O3- and Cu3O4- are weak. The calculated NICS(0) and NICS(1) values of Cu3O3- are -25.0 ppm and -19.2 ppm, respectively, and those of Cu3O4- are -18.6 ppm and -10.5 ppm, respectively, indicating that they both are significantly aromatic.
RESUMO
HYPOTHESIS: Although a raspberry-like configuration has been long observed in biological processes (e.g., the intimate association between Cajal bodies and B-snurposomes), studies on this morphology are very limited. Raspberry-like droplets created with multiple immiscible liquids are expected to provides an ideal model for such structures in biological systems, including their possible formation mechanism, phase behaviors, and coalescence dynamics. EXPERIMENTS & SIMULATIONS: Using three liquid phases, one surfactant and some colloidal particles, raspberry-like droplets containing one large central droplet and multiple protrusions embedded on its surface were successfully created. Confocal microscopy studies were carried out to track their formation and coalescence dynamics. A 2D phase-field model was applied to test the influence of the protrusions in the system. FINDINGS: The formation of this raspberry-like morphology involves a partial inversion process, which was predicted by Friberg et al. with numerical simulations but has never been demonstrated experimentally. A two-step coalescence was revealed, where the protrusions merge first and create a capillary bridge, which drives the droplets to coalesce. Increasing the viscosity of the continuous phase can help to prevent the destabilization. These fundamental features of raspberry-like droplets represent an important step toward producing multi-liquid materials with unique functionality, and can potentially illuminate some biological systems and processes.