Branch-Chain-Rich Diisopropyl Ether with Steric Hindrance Facilitates Stable Cycling of Lithium Batteries at-20℃

Li metal batteries(LMBs)offer signifi-cant potential as high energy density alternatives;nev-ertheless,their performance is hindered by the slow desolvation process of electrolytes,particularly at low temperatures(LT),leading to low coulombic efficiency and limited cycle stability.Thus,it is essential to opti-mize the solvation structure thereby achieving a rapid desolvation process in LMBs at LT.Herein,we introduce branch chain-rich diisopropyl ether(DIPE)into a 2.5 M Li bis(fluorosulfonyl)imide dipropyl ether(DPE)elec-trolyte as a co-solvent for high-performance LMBs at-20℃.The incorporation of DIPE not only enhances the disorder within the electrolyte,but also induces a steric hindrance effect form DIPE’s branch chain,excluding other solvent molecules from Li+solvation sheath.Both of these factors contribute to the weak interactions between Li^(+)and solvent molecules,effectively reducing the desolvation energy of the electrolyte.Consequently,Li(50μm)||LFP(mass loading~10 mg cm^(-2))cells in DPE/DIPE based electrolyte demonstrate stable performance over 650 cycles at-20℃,delivering 87.2 mAh g^(-1),and over 255 cycles at 25℃ with 124.8 mAh g^(-1).DIPE broadens the electrolyte design from molecular structure considera-tions,offering a promising avenue for highly stable LMBs at LT.

Steric hindrance shielding viologen against alkali attack in realizing ultrastable aqueous flow batteries

Viologens known as a kind of promising negolyte materials for aqueous organic redox flow batteries,face a critical stability challenge due to the S_N2 nucleophilic attack by hydroxide ions(OH-)during the battery cycling.In this work,a N-cyclic quaternary ammonium-grafted viologen molecule,viz.1,1'-bis(4,4'-dime thylpiperidiniumyl)-4,4'-bipyridinium tetrachloride((DBPPy)Cl_(4)),is developed by the molecular engineering strategy.The obtained(DBPPy)Cl_(4) molecule shows a decent solubility of 1.84 M and a redox potential of-0.52 V vs.Ag/AgCl,Experimental and theoretical results reveal that the grafted N-cyclic quaternary ammonium groups act as the steric hindrance to prevent nucleophilic attack by OH~-,increasing the alkali resistance of the electroactive molecule.The symmetrical battery with 0.50 M(DBPPy)Cl4shows negligible decay during the 13-day cycling test.As demonstration,the flow battery utilizing 1.0 M(DBPPy)Cl_(4) as the negolyte and 1-(1-oxyl-2,2',6,6'-tetramethylpiperidin-4-yl)-1'-(3-(trimethylammonio)propyl)-4,4'-bipyridinium trichloride as the posolyte exhibits a high capacity retention rate of 99.99%per cycle at 60 mA cm^(-2).

Nickel catalysts with asymmetric steric hindrance for ethylene polymerization

α-Diimide catalysts have attracted widespread attention due to their unique chain walking characteristics.A series ofα-diimide nickel/palladium catalysts with different electronic effects and steric hindrances were designed and synthesized for olefin polymerization.In this work,we synthesized a series of asymmetricα-diimide nickel complexes with different steric hindrances and used them for ethylene polymerization.These nickel catalysts have high ethylene polymerization activity,up to 6.51×10^(6)g·mol^(−1)·h^(−1),and the prepared polyethylene has a moderate melting point and high molecular weight(up to 38.2×10^(4)g·mol^(−1)),with a branching density distribution between 7 and 94 branches per 1000 carbons.More importantly,the polyethylene prepared by these catalysts exhibits excellent tensile properties,with strain and stress reaching 800%and 30 MPa,respectively.

Unraveling abnormal buried interface anion defect passivation mechanisms depending on cation-induced steric hindrance for efficient and stable perovskite solar cells

Although ionic liquids(ILs)have been widely employed to heal the defects in perovskite solar cells(PSCs),the corresponding defect passivation mechanisms are not thoroughly understood up to now.Herein,we first reveal an abnormal buried interface anion defect passivation mechanism depending on cationinduced steric hindrance.The IL molecules containing the same anion([BF4]^(-))and different sizes of imidazolium cations induced by substituent size are used to manipulate buried interface.It was revealed what passivated interfacial defects is mainly anions instead of cations.Theoretical and experimental results demonstrate that the large-sized cations can weaken the ionic bond strength between anions and cations,and facilitate the interaction between anions and SnO2as well as perovskites,which is conducive to interfacial defect passivation and ameliorating interfacial contact.It can be concluded that interfacial chemical interaction strength and defect passivation effect are positively correlated with the size of cations.The discovery breaks conventional thinking that large-sized modification molecules would weaken their chemical interaction with perovskite.Compared with the control device(21.54%),the device based on 1,3-Bis(1-adamantyl)-imidazolium tetrafluoroborate(BAIMBF4)with maximum size cations achieves a significantly enhanced efficiency of 23.61%along with much increased moisture,thermal and light stabilities.

Influence of Steric Hindrance Between Hydrogen Atoms of Linkage Groups and Adjacent Phenyls on Properties of Polyimide

A diamine monomer 4,4′-methylenedianiline（MDA） was introduced to modify the polyimide of pyromellitic dianhydride（PMDA） and 4,4′-oxydianiline（ODA） by polycondensation. A series of polyamic acids was synthesized from MDA and ODA of different molar ratios with PMDA of sum mole of moles of MDA and ODA, and polyimide films were obtained by thermal imidization. Polyimide（PI） films were characterized by tensile testing, dynamic mechanical analysis（DMA）, thermal gravimetry analysis（TGA）, Fourier transform infrared spectroscopy （FTIR）, wide X-ray diffraction（WAXD） and molecular simulation. With the increase of MDA content, the tensile strength and thermal decomposition temperature remained generally stable compared with those of PMDA/ODA polyimide. Unexpectedly, the glass transition temperature（Tg） and Young＇s modulus increased from 388.7 °C and 2.37 GPa to 408.3 °C and 5.74 GPa, respectively. The results of WAXD and molecular simulation indicate the steric hindrance among hydrogen atoms of the linkage groups and adjacent phenyls enhanced the properties of the polyimide modified with MDA.

Steric hindrance induced low exciton binding energy enables low-driving-force organic solar cells

Exciton binding energy(E_(b))has been regarded as a critical parameter in charge separation during photovoltaic conversion.Minimizing the E_(b) of the photovoltaic materials can facilitate the exciton dissociation in low-driving force organic solar cells(OSCs)and thus improve the power conversion efficiency(PCE);nevertheless,diminishing the E_(b) with deliberate design principles remains a significant challenge.Herein,bulky side chain as steric hindrance structure was inserted into Y-series acceptors to minimize the E_(b) by modulating the intra-and intermolecular interaction.Theoretical and experimental results indicate that steric hindrance-induced optimal intra-and intermolecular interaction can enhance molecular polarizability,promote electronic orbital overlap between molecules,and facilitate delocalized charge trans-fer pathways,thereby resulting in a low E_(b).The conspicuously reduced E_(b) obtained in Y-ChC5 with pinpoint steric hindrance modulation can minimize the detrimental effects on exciton dissociation in low-driving-force OSCs,achieving a remarkable PCE of 19.1%with over 95%internal quantum efficiency.Our study provides a new molecular design rationale to reduce the E_(b).

Steric hindrance effect of Schiff-base ligands on magnetic relaxation dynamics and emissive behavior of two dinuclear dysprosium complexes

The self-assembly reactions between mixed-ligand and tetrahydrate dysprosium acetate in the presence of mixed organic solvents lead to two structural similar dinuclear dysprosium complexes with composition formulas of Dy_(2)(L_1)_(2)(L_(2))_(2)(CH_(3)OH)_(2)·CH_(2)Cl_(2)·CH_(3)OH(1) and Dy_(2)(L_1)_(2)(L_(3))_(2)(CH_(3)OH)_(2)·CH_(3)CN(2),where L_1,L_(2) and L_(3) represent the deprotonated form of 4-tert-butyl-2-(7-methoxybenzo[d]oxazol-2-yl)phenol,(E)-1-(((3,5-di-tert-butyI-2-hydroxyphenyI)imino)methyl)naphthalen-2-ol and(E)-2,4-di-tertbutyl-6-((2-hydroxybenzylidene)amino)phenol.The tiny difference of the core structure of 1 and 2 is derived from the steric hindrance of Schiff base ligands L_(2) and L_(3).Dynamic magnetic measurements reveal that 1 and 2 show frequency-dependent out-of-phase alternating-current susceptibility signal peaks at different temperatures under zero dc field,diagnostic of single-molecule magnet behavior.The experimental derived energy barrier to magnetization reversal for 1 and 2 is 108(1),47(2) and 33(3) K.Ab initio CASSCF calculations performed on 1 and 2 suggest that the origin of the difference in magnetic properties originates from the variation in the single-ion anisotropy that arises due to minor structural variation.Further,the equation to calculate the effective energy barrier for Dy_(2) proposed earlier is found to yield an excellent agreement with the experimental results.Solid state fluorescence measurements performed on 1 and 2 demonstrate that both exhibit two ligands centered components of fluorescent emissive,in addition,with different emitting colors and chromaticity coordinates.The discrepancy of fluorescence and single molecule magnet behavior showed by 1 and 2 can be attributed to the steric hindrance effect of Schiff base ligands.

The Influence of Various Cationic Group on Polynorbornene Based Anion Exchange Membranes with Hydrophobic Large Steric Hindrance Arylene Substituent

A series of brominated polynorbornene derivatives,including bulky steric hydrophobic groups and highly physical and chemical stable backbones,were synthesized via ring-opening metathesis polymerization and post-functionalized with trimethylammonium(QA),N-methylimidazole(Im),N-methylpyrrolidinium(Pyr)or N-methylpiperidinium(Pip)to construct the entire anion exchange membranes(AEMs).Benefited from prominent phase-separated morphology,PBO-x%-y(x=66,68,70;y=QA,Im,Pyr,Pip)AEMs with ion exchange capacity(IEC)approaching 2.0 meq·g^(−1)exhibited super high hydroxide conductivities.Thereinto,PBO-70%-Pip possessed the highest hydroxide conductivity of 137.3 mS·cm^(−1)at 80℃Moreover,all membranes exhibit low swelling ratio(SR)(the SR of PBO-66%-QA was just 8.6%at 80℃).That is,bulky steric hydrophobic groups play a crucial role in balancing the high hydroxide conductivity and low SR in AEMs.Furthermore,three AEMs(PBO-66%-QA,PBO-68%-Pyr,PBO-70%-Pip)showed good alkaline stability after immersion into 1.0 mol/L NaOH aqueous solution at 80℃for 480 h without any degradation.

Tailoring the microstructure and properties of PES/SPSf loose nanofiltration membranes using SPES as a hydrophilic polymer for the effective removal of dyes via steric hindrance and charge effect

Herein,polyethersulfone(PES)and sulfonated polysulfone(SPSf)blend membranes were prepared with addition of sulfonated polyethersulfone(SPES)as a hydrophilic polymer and adipic acid as a porogen via non-solvent induced phase separation method for effective fractionation of dyes based on the influence of steric hindrance and charge effect.Raman spectroscopy and molecular dynamic simulation modeling confirmed that hydrogen bonds between PES,SPSf,SPES,and adipic acid were crucial to membrane formation and spatial arrangement.Further addition of hydrophilic SPES resulted in a membrane with reduced pore size and molecular weight cut-off as well as amplified negative charge and pure water permeance.During separation,the blend membranes exhibited higher rejection rates for nine types of small molecular weight(269.3–800 Da)dyes than for neutral polyethylene glycol molecules(200–1000 Da).This was attributed to the size effect and the synergistic effect between steric hindrance and charge repulsion.Notably,the synergistic impact decreased with dye molecular weight,while greater membrane negative charge enhanced small molecular dye rejection.Ideal operational stability and anti-fouling performance were best observed in M2(PES/SPSf/SPES,3.1 wt%).Summarily,this study demonstrates that SPES with–SO3‒functional groups can be applied to control the microstructure and separation of membranes.

Steric Hindrance Ligand Strategy to Aluminum Porphyrin Catalyst for Completely Alternative Copolymerization of CO_2 and Propylene Oxide

Aluminum porphyrin complexes are heavy-metal-free and soil-tolerant green catalysts for the copolymerization of CO2 and propylene oxide（PO）, but they suffer from relatively poor poly（propylene carbonate）（PPC） selectivity. Herein, steric hindrance porphyrin ligand was used to enhance the PPC selectivity. Typically, a bulky anthracene-like group was incorporated into the porphyrin ring to form 5,10,15,20-tetra（1,2,3,4,5,6,7,8-octahydro-1,4：5,8-dimethanoanthracen-9-yl）porphyrin, the aluminum porphyrin complex with this ligand, in combination with bis（triphenylphosphine）iminium chloride as a co-catalyst, produced completely alternate PPC. Additionally, the obtained PPC showed high regioselectivity, with a head-to-tail linkage content（HT） of 92%. Therefore, we demonstrated that introduction of bulky steric ligand into the porphyrin ring could reduce the propylene oxide homopolymerization activity leading to excellent PPC selectivity, and improve regioselectivity for the PO ring-opening during the copolymerization.

Carbazole-endcapped Spiro[fluorene-9,9＇-xanthene] with Large Steric Hindrance as Hole-transporting Host for Heavily-doped and High Performance OLEDs

In this work, we designed and synthesized a novel spirocyclic compound functionalized spiro[fluorene-9,9＇- xanthene] with carbazole group （2-carbazolyl-spiro[fluorene-9,9＇-xanthene], SFX-Cz） via Friedel-Crafts and Ullmann reaction, which is expected to own high thermal and morphological stability, and good carrier injection/ transporting properties due to the excellent hole transporting characteristics of carbazole and cruciform structure of spiro[fluorene-9,9＇-xanthene]. The carbazole end-capped spiro[fluorene-9,9＇-xanthene] SFX-Cz based PhOLEDs with Flrpic as phosphor emitter have been researched by varying dopant concentration, which exhibit the maximum EQEs of 8.9%, 7.4%, 9.1%, and 4.7% with the doping increasing from 10% to 50%. The higher performance PhOLEDs are independent on concentration variation from 10% to 30%, which suggests the bulky steric hindrance of SFX-Cz might be a potential canditate for high performance and inexpensive device with simplified process.

Size matters:Steric hindrance of precursor molecules controlling the evolution of CdSe magic-size clusters and quantum dots

Little is known about how to precisely promote the selective production of either colloidal semiconductor metal chalcogenide(ME),magic-size clusters(MSCs),or quantum dots(QDs).Recently,a two-pathway model has been proposed to comprehend their evolution;here,we reveal for the first time that the size of precursors plays a decisive role in the selected evolution pathway of MSCs and QDs.With the reaction of cadmium myristate(Cd(MA)2)and tri-n-octylphosphine selenide(SeTOP)in 1-octadecene(ODE)as a model system,the size of Cd precursors was manipulated by the steric hindrance of carboxylic acid(RCOOH)additive.Without RCOOH,the reaction produced both CdSe MSCs and QDs(from 100 to 240℃).With RCOOH,the reaction produced MSCs or QDs when R was small(such as CH3−)or large(such as C6H5−),respectively.According to the twopathway model,the selective evolution is attributed to the promotion and suppression of the self-assembly of Cd and Se precursors,respectively.We propose that the addition of carboxylic acid may occur ligand exchange with Cd(MA)2,causing the different sizes of Cd precursor.The results suggest that the size of Cd precursors regulates the self-assemble behavior of the precursors,which dictates the directed evolution of either MSCs or QDs.The present findings bring insights into the two-pathway model,as the size of M and E precursors determine the evolution pathways of MSCs or QDs,the understanding of which is of great fundamental significance toward mechanism-enabled design and predictive synthesis of functional nanomaterials.

High-performance nonfused ring electron acceptor with a steric hindrance induced planar molecular backbone

Three nonfused ring electron acceptors (NFREAs) TTC6,TT-C8T and TT-TC8 were purposefully designed and synthesized.The molecular geometry can be adjusted by the steric hindrance of lateral substituents.According to the DFT calculations,from TTC6 to TT-C8T and TT-TC8,planarity of the molecular backbone is gradually improved,accompanying with the enhancing of intramolecular charge transfer effect.As for TT-TC8,the two phenyl substituents are almost perpendicular to the molecular backbone,which endues the acceptor with good solubility and suppresses it to form over-aggregation.Multidirectional regular molecular orientation and closer molecular stacking are formed in TT-TC8 film.As a result,TT-TC8 based devices afford the highest PCE of 13.13%,which is much higher than that of TTC6 (4.41%) and TT-C8T (10.42%) and among the highest PCE values based on NFREAs.

Topology control of three-dimensional covalent organic frameworks by adjusting steric hindrance effect

Since the intrinsic topological network determines their pore characteristics and functional applications, it is important to construct 3D COFs with target topology from predesigned functional building blocks. However, when starting from precursors with same connectivity but different bulky groups, the structure and topology of 3D COFs may change, which will greatly increase the complexity of the crystal structure determination. Therefore, it is essential to understand how to control the steric hindrance effects and synthesize 3D COFs with target topology. Herein, we report the topology control of 3D COFs by adjusting steric hindrance effects of functional building blocks. Starting from a quadrilateral building block with sterically hindered phenyl groups, we have been able to achieve the target pts topology instead of the unprecedented ljh network that we reported recently by elongating the tetrahedral building block. This result clearly shows that it is promising to precisely control the topology of 3D COFs by judiciously selecting building blocks with steric hindrance and suitable dimensions.

Steric Hindrance Effect in High-Temperature Reactions

High-temperature reactions widely exist in nature.However,they are difficult to characterize either experimentally or computationally.The minimum energy path(MEP)model routinely used in computational modeling of chemical reactions is not justified to describe high-temperature reactions since high-energy structures are actively involved at high temperatures.In this study,we used methane(CH4)decomposition on Cu(111)surface as an example to compare systematically results obtained from the MEP model with those obtained from an explicit sampling of all relevant structures via ab initio molecular dynamics(AIMD)simulations at different temperatures.Interestingly,we found that,for reactions protected by strong steric hindrance effects,the MEP was still followed effectively even at a temperature close to the Cu melting point.In contrast,without such protection,the flexibility of the surface Cu atoms could lead to a significant reduction of the free-energy barrier at a high temperature.Accordingly,some earlier conclusions made about graphene growth mechanisms based on MEP calculations should be revisited.The physical insights provided by this study could deepen our understanding of high-temperature surface reactions.

Cold plasma-activated Cu-Co catalysts with CN vacancies for enhancing CO_(2)electroreduction to low-carbon alcohol

Electrocatalytic CO_(2)reduction reaction to low-carbon alcohol is a challenging task,especially high selectivity for ethanol,which is mainly limited by the regulation of reaction intermediates and subsequent C–C coupling.A Cu-Co bimetallic catalyst with CN vacancies is successfully developed by H_(2)cold plasma toward a high-efficiency CO_(2)RR into low-carbon alcohol.The Cu-Co PBA-V_(CN)(Prussian blue analogues with CN vacancies)electrocatalyst yields methanol and ethanol as major products with a total low-carbon alcohol FE of 83.8%(methanol:39.2%,ethanol:44.6%)at-0.9 V vs.RHE,excellent durability(100 h)and a small onset potential of-0.21 V.ATR-SEIRAS(attenuated total internal reflection surface enhanced infrared absorption spectroscopy)and DFT(density functional theory)reveal that the steric hindrance of V_(CN)can enhance the CO generation from*COOH,and the C–C coupling can also be increased by CO spillover on uniformly dispersed Cu atoms.This work provides a strategy for the design and preparation of electrocatalysts for CO_(2)RR into low-carbon alcohol products and highlights the impact of catalyst steric hindrance to catalytic performance.

A Novel Initiator Containing Alkyne Group for the Polymerization of 2-Ethyl-2-oxazoline

A novel trifunctional initiator with one alkyne and two trifluoromethanesulfonate moieties was synthesized from a protected alcohol 5-hydroxyl-2-phenyl-1, 3-dioxane. The alkyne func- tionalized intermediate with two protected alcohol groups was synthesized by reacting with propargyl bromide. The alcohol groups were cleaved using a mixture of tetrahydrofuran and hydrochloric acid aqueous solution. In the last step the initiator was synthesized us- ing triflic anhydride in carbon tetrachloride. The initiator was characterized by 1H NMR and used for the polymerization of 2-ethyl-2-oxazoline which gives polymers with narrow distribution. For comparison a similar initiator with two tosylates was prepared and used for the polymerization of the monomer 2-ethyl-2-oxazoline, the resulting product has a wide molecular weight distribution and most of the initiator remains unreacted after 24 h which may be due to the steric hindrance between the two tosylate groups. To further explore the steric hindrance phenomenon, a linear tosylate initiator was synthesized, but still some of the initiator remains unreacted, illustrating that both steric hindrance and electrophilic balance affect the efficiency of the cationic ring-opening polymerization. All of the polymers were characterized in detail by using IH NMR, matrix-assisted laser desorption/ionization time-of-flight mass spectroscopy, and size exclusion chromatography to confirm the purity and distribution of the polymers.

Estimation of Separation of Electrolytes and Organic Compounds by Nanofiltration Membranes Using an Irreversible Thermodynamic Modei

Nanofiltration separation has become a popular technique for removing largeorganic molecules and inorganic substances from water. It is achieved by a combination of threemechanisms: electrostatic repulsion, sieving and diffusion. In the present work, a model based onirreversible thermodynamics is extended and used to estimate rejection of inorganic salts andorganic substances. Binary systems are modeled, where the feed contains an ion that is much lesspermeable to the membrane as compared with the other ion. The two model parameters are estimated byfitting the model to the experimental data. Variation of these parameters with the composition ofthe feed is described by an empirical correlation. This work attempts to describe transport throughthe nanofiltration membranes by a simple model.

Synthesis and DFT Calculation of a Four- coordinated Manganese Compound Mn_2(BPTC)

A new four-coordinated manganese compound Mn2（BPTC） （BPTC =- biphenyl- 2,4,4＇,6-tetracarboxylate） with flu topology net was synthesized under hydrothermal conditions. Single-crystal X-ray diffraction analysis confirms its crystal belongs to the monoclinic system, space group C2/c with a = 12.2092（11）, b = 14.6932（9）, c = 8.9998（10） A, t= 108.256（12）°, Z= 4, V= 1533.2（2） A3, Dc = 1.889 mg/m3,μ = 1.69, F（O00） = 864, the final R = 0.063 and wR = 0.201 for 1407 observed reflections （I 〉 20（/））. UV-Vis absorption spectrum shows the title compound has a strong absorption at 326 and 238 nm and the optical diffuse reflectance determination shows the band gap of the title compound is 3.15 eV. The theory calculation elucidated that the UV absorptions of the title compound mainly arise from the electron transition from bonding orbitals of BPTC4- ligand to the empty orbitals of BPTC4- and Mn（II） ions.

SYNTHESIS AND FREE RADICAL RING-OPENING POLYMERIZATION OF 2-METHYL-AND 2-METHYL-9-n-BUTYL-(-7-METHYLENE-1,4,6-TRIOXA-SPIRO (4, 4)NONANE)

This paper describes the synthesis and free radical ring-opening polymerization of 2-methyl-and 2-methyl-9-n-butyl (-7-methylene-1, 4, 6-trioxaspiro (4, 4) nonane). The structures of the two polymers were verified by IR, 'H and ^(13)C NMR spectra. The substituent on 9-position of 7-methylene-trioxaspiro (4, 4) nonane affects the structure of polymer and polymerization activity. The polymerization mechanism is discussed.