Showing papers on "Lewis acids and bases published in 2018"

Incorporation of Imidazolium-Based Poly(ionic liquid)s into a Metal–Organic Framework for CO2 Capture and Conversion

Abstract: The rational integration of multiple functional components into a composite material could result in enhanced activity tailored for specific applications. Herein, imidazolium-based poly(ionic liquid)s (denoted as polyILs) have been confined into the metal–organic framework (MOF) material MIL-101 via in situ polymerization of encapsulated monomers. The resultant composite polyILs@MIL-101 exhibits good CO2 capture capability that is beneficial for the catalysis of the cycloaddition of CO2 with epoxides to form cyclic carbonates at subatmospheric pressure in the absence of any cocatalyst. The significantly enhanced activity of polyILs@MIL-101, compared to either MIL-101 or polyILs, is attributed to the synergistic effect among the good CO2 enrichment capacity, the Lewis acid sites in the MOF, as well as the Lewis base sites in the polyILs.

Tuning Molecular Interactions for Highly Reproducible and Efficient Formamidinium Perovskite Solar Cells via Adduct Approach

Abstract: The Lewis acid–base adduct approach has been widely used to form uniform perovskite films, which has provided a methodological base for the development of high-performance perovskite solar cells. However, its incompatibility with formamidinium (FA)-based perovskites has impeded further enhancement of photovoltaic performance and stability. Here, we report an efficient and reproducible method to fabricate highly uniform FAPbI3 films via the adduct approach. Replacement of the typical Lewis base dimethyl sulfoxide (DMSO) with N-methyl-2-pyrrolidone (NMP) enabled the formation of a stable intermediate adduct phase, which can be converted into a uniform and pinhole-free FAPbI3 film. Infrared and computational analyses revealed a stronger interaction between NMP with the FA cation than DMSO, which facilitates the formation of a stable FAI·PbI2·NMP adduct. On the basis of the molecular interactions with different Lewis bases, we proposed criteria for selecting the Lewis bases. Owed to the high film quality, per...

Suppressing defects through the synergistic effect of a Lewis base and a Lewis acid for highly efficient and stable perovskite solar cells

Abstract: Achieving long-term operational stability at a high efficiency level for perovskite solar cells is the most challenging issue toward commercialization of this emerging photovoltaic technology. Here, we investigated the cooperation of a Lewis base and a Lewis acid by combining commercial bis-PCBM mixed isomers as the Lewis acid in the antisolvent and N-(4-bromophenyl)thiourea (BrPh-ThR) as the Lewis base in the perovskite solution precursor. The combination of the Lewis base and the Lewis acid synergistically passivates Pb2+ and PbX3− antisite defects, enlarges the perovskite grain size, and improves charge-carrier separation and transport, leading to improved device efficiency from 19.3% to 21.7%. In addition, this Lewis base and acid combination also suppresses moisture incursion and passivates pinholes generated in the hole-transporting layer. The unsealed devices remained at 93% of the initial efficiency value in ambient air (10–20% relative humidity) after 3600 h at 20–25 °C and dropped by 10% after 1500 h under continuous operation at 1-sun illumination and 55 °C in nitrogen with maximum power-point tracking.

Synthesis, structure and reaction chemistry of a nucleophilic aluminyl anion

Abstract: The reactivity of aluminium compounds is dominated by their electron deficiency and consequent electrophilicity; these compounds are archetypal Lewis acids (electron-pair acceptors). The main industrial roles of aluminium, and classical methods of synthesizing aluminium–element bonds (for example, hydroalumination and metathesis), draw on the electron deficiency of species of the type AlR3 and AlCl31,2. Whereas aluminates, [AlR4]−, are well known, the idea of reversing polarity and using an aluminium reagent as the nucleophilic partner in bond-forming substitution reactions is unprecedented, owing to the fact that low-valent aluminium anions analogous to nitrogen-, carbon- and boron-centred reagents of the types [NX2]−, [CX3]− and [BX2]− are unknown3–5. Aluminium compounds in the +1 oxidation state are known, but are thermodynamically unstable with respect to disproportionation. Compounds of this type are typically oligomeric6–8, although monomeric systems that possess a metal-centred lone pair, such as Al(Nacnac)Dipp (where (Nacnac)Dipp = (NDippCR)2CH and R = tBu, Me; Dipp = 2,6-iPr2C6H3), have also been reported9,10. Coordination of these species, and also of (η5-C5Me5)Al, to a range of Lewis acids has been observed11–13, but their primary mode of reactivity involves facile oxidative addition to generate Al(iii) species6–8,14–16. Here we report the synthesis, structure and reaction chemistry of an anionic aluminium(i) nucleophile, the dimethylxanthene-stabilized potassium aluminyl [K{Al(NON)}]2 (NON = 4,5-bis(2,6-diisopropylanilido)-2,7-di-tert-butyl-9,9-dimethylxanthene). This species displays unprecedented reactivity in the formation of aluminium–element covalent bonds and in the C–H oxidative addition of benzene, suggesting that it could find further use in both metal–carbon and metal–metal bond-forming reactions. An aluminium compound is synthesized in which the aluminium is formally anionic; reactions with various substrates suggest that this compound acts as the nucleophilic partner in both metal–carbon and metal–metal bond-forming reactions.

Structure–performance descriptors and the role of Lewis acidity in the methanol-to-propylene process

Abstract: The combination of well-defined acid sites, shape-selective properties and outstanding stability places zeolites among the most practically relevant heterogeneous catalysts. The development of structure–performance descriptors for processes that they catalyse has been a matter of intense debate, both in industry and academia, and the direct conversion of methanol to olefins is a prototypical system in which various catalytic functions contribute to the overall performance. Propylene selectivity and resistance to coking are the two most important parameters in developing new methanol-to-olefin catalysts. Here, we present a systematic investigation on the effect of acidity on the performance of the zeolite ‘ZSM-5’ for the production of propylene. Our results demonstrate that the isolation of Bronsted acid sites is key to the selective formation of propylene. Also, the introduction of Lewis acid sites prevents the formation of coke, hence drastically increasing catalyst lifetime.

Realizing Efficient Lead-Free Formamidinium Tin Triiodide Perovskite Solar Cells via a Sequential Deposition Route

Abstract: Recently, the evolved intermediate phase based on iodoplumbate anions that mediates perovskite crystallization has been embodied as the Lewis acid-base adduct formed by metal halides (serve as Lewis acid) and polar aprotic solvents (serve as Lewis base). Based on this principle, it is proposed to constitute efficient Lewis acid-base adduct in the SnI2 deposition step to modulate its volume expansion and fast reaction with methylammonium iodide (MAI)/formamidinium iodide (FAI) (FAI is studied hereafter). Herein, trimethylamine (TMA) is employed as the additional Lewis base in the tin halide solution to form SnY2 -TMA complexes (Y = I- , F- ) in the first-step deposition, followed by intercalating with FAI to convert into FASnI. It is shown that TMA can facilitate homogeneous film formation of a SnI2 (+SnF2 ) layer by effectively forming intermediate SnY2 -TMA complexes. Meanwhile, its relatively larger size and weaker affinity with SnI2 than FA+ ions will facilitate the intramolecular exchange with FA+ ions, thereby enabling the formation of dense and compact FASnI3 film with large crystalline domain (>1 µm). As a result, high power conversion efficiencies of 4.34% and 7.09% with decent stability are successfully accomplished in both conventional and inverted perovskite solar cells, respectively.

Manganese-catalysed benzylic C(sp 3)-H amination for late-stage functionalization

Abstract: Reactions that directly install nitrogen into C-H bonds of complex molecules are significant because of their potential to change the chemical and biological properties of a given compound. Although selective intramolecular C-H amination reactions are known, achieving high levels of reactivity while maintaining excellent site selectivity and functional-group tolerance remains a challenge for intermolecular C-H amination. Here, we report a manganese perchlorophthalocyanine catalyst [MnIII(ClPc)] for intermolecular benzylic C-H amination of bioactive molecules and natural products that proceeds with unprecedented levels of reactivity and site selectivity. In the presence of a Bronsted or Lewis acid, the [MnIII(ClPc)]-catalysed C-H amination demonstrates unique tolerance for tertiary amine, pyridine and benzimidazole functionalities. Mechanistic studies suggest that C-H amination likely proceeds through an electrophilic metallonitrene intermediate via a stepwise pathway where C-H cleavage is the rate-determining step of the reaction. Collectively, these mechanistic features contrast with previous base-metal-catalysed C-H aminations and provide new opportunities for tunable selectivities.

Polymerization of Polar Monomers Mediated by Main-Group Lewis Acid-Base Pairs.

Abstract: The development of new or more sustainable, active, efficient, controlled, and selective polymerization reactions or processes continues to be crucial for the synthesis of important polymers or materials with specific structures or functions. In this context, the newly emerged polymerization technique enabled by main-group Lewis pairs (LPs), termed as Lewis pair polymerization (LPP), exploits the synergy and cooperativity between the Lewis acid (LA) and Lewis base (LB) sites of LPs, which can be employed as frustrated Lewis pairs (FLPs), interacting LPs (ILPs), or classical Lewis adducts (CLAs), to effect cooperative monomer activation as well as chain initiation, propagation, termination, and transfer events. Through balancing the Lewis acidity, Lewis basicity, and steric effects of LPs, LPP has shown several unique advantages or intriguing opportunities compared to other polymerization techniques and demonstrated its broad polar monomer scope, high activity, control or livingness, and complete chemo- or...

Frustrated Lewis Pairs Catalyzed Asymmetric Metal-Free Hydrogenations and Hydrosilylations.

Abstract: ConspectusThe use of frustrated Lewis pairs is an extremely important approach to metal-free hydrogenations. In contrast to the rapid growth of catalytic reactions, asymmetric hydrogenations are far less developed due to a severe shortage of readily available chiral frustrated Lewis pair catalysts with high catalytic activities and selectivities. Unlike the stable Lewis base component of frustrated Lewis pairs, the moisture-sensitive boron Lewis acid component is difficult to prepare. The development of convenient methods for the quick construction of chiral boron Lewis acids is therefore of great interest.In this Account, we summarize our recent studies on frustrated Lewis pair-catalyzed, asymmetric metal-free hydrogenations and hydrosilylations. To address the shortage of highly active and selective catalysts, we developed a novel strategy for the in situ preparation of chiral boron Lewis acids by the hydroboration of chiral dienes or diynes with Piers’ borane without further purification, which allows ...

Lewis Superacids: Classifications, Candidates, and Applications.

Abstract: Lewis acids play a major role in all areas of chemistry. For a long time, toxic, corrosive and oxidizing SbF5 was considered as the strongest Lewis acid known. Lately, species significantly exceeding the Lewis acidity of SbF5 have been realized and were termed Lewis superacids (LSA). Prospective new candidates emerge steadily, which not only outperform SbF5 by their strength, but also in terms of their accessibility and ease of handling. In principle, Lewis superacids allow us to combine the outstanding activity of Bronsted superacids with the excellent selectivity of a common Lewis acid. However, the broad application of Lewis superacids in synthesis is all but popular. The present review deals with strong Lewis acids. First, it critically discusses Lewis acidity scaling methods and suggests an extended definition for Lewis superacidity. It then summarizes the properties and applications of the strongest currently known Lewis acids, indexed by the fluoride ion affinity (FIA). The supporting information contains a comprehensive list of experimentally and theoretically derived FIA data as a guide for the choice of Lewis acidic reagents/catalyst. This contribution shall encourage the search for new Lewis superacids and promote their application in non-specialized laboratories.

Robust Bifunctional Lanthanide Cluster Based Metal-Organic Frameworks (MOFs) for Tandem Deacetalization-Knoevenagel Reaction.

Abstract: A series of 12-connected lanthanide cluster based metal–organic frameworks (MOFs) have been constructed by [Ln6(μ3-OH)8(COO−)12] secondary building units (SBUs) and 2-aminobenzenedicarboxylate (BDC-NH2) ligands. These obtained materials exhibit high chemical stability and generic thermal stability, especially in acidic and basic conditions. They also present commendable CO2 adsorption capacity, and Yb-BDC-NH2 was further confirmed by a breakthrough experiment under both dry and wet conditions. Moreover, these materials possess both Lewis acid and Bronsted base sites that can catalyze one-pot tandem deacetalization–Knoevenagel condensation reactions.

Selective C−N Borylation of Alkyl Amines Promoted by Lewis Base

Abstract: An efficient method for the metal-free deaminative borylation of alkylamines, using bis(catecholato)diboron as the boron source, to directly synthesize various alkyl potassium trifluoroborate salts is introduced. The key to this high reactivity is the utilization of pyridinium salt activated alkylamines, with a catalytic amount of a bipyridine-type Lewis base as a promoter. This transformation shows good functional-group compatibility (e.g., it is unimpeded by the presence of a ketone, indole, internal alkene, or unactivated alkyl chloride) and can serve as a powerful synthetic tool for borylation of amine groups in complex compounds. Mechanistic experiments and computations suggest a mechanism in which the Lewis base activated B2 cat2 unit intercepts an alkyl radical generated by single-electron transfer (SET) from a boron-based reductant.

Aerobic Oxidation of 5-(Hydroxymethyl)furfural Cyclic Acetal Enables Selective Furan-2,5-dicarboxylic Acid Formation with CeO2-Supported Gold Catalyst

Abstract: The utilization of 5-(hydroxymethyl)furfural (HMF) for the large-scale production of essential chemicals has been largely limited by the formation of solid humin as a byproduct, which prevents the operation of stepwise batch-type and continuous flow-type processes. The reaction of HMF with 1,3-propanediol produces an HMF acetal derivative that exhibits excellent thermal stability. Aerobic oxidation of the HMF acetal with a CeO2-supported Au catalyst and Na2CO3 in water gives a 90–95 % yield of furan 2,5-dicarboxylic acid, an increasingly important commodity chemical for the biorenewables industry, from concentrated solutions (10–20 wt %) without humin formation. The six-membered acetal ring suppresses thermal decomposition and self-polymerization of HMF in concentrated solutions. Kinetic studies supported by DFT calculations identify two crucial steps in the reaction mechanism, that is, the partial hydrolysis of the acetal into 5-formyl-2-furan carboxylic acid involving OH− and Lewis acid sites on CeO2, and subsequent oxidative dehydrogenation of the in situ generated hemiacetal involving Au nanoparticles. These results represent a significant advance over the current state of the art, overcoming an inherent limitation of the oxidation of HMF to an important monomer for biopolymer production.

Acid-Promoter-Free Ethylene Methoxycarbonylation over Ru-Clusters/Ceria: The Catalysis of Interfacial Lewis Acid–Base Pair

Abstract: The interface of metal-oxide plays pivotal roles in catalytic reactions, but its catalytic function is still not clear. In this study, we report the high activity of nanostructured Ru/ceria (Ru-clusters/ceria) in the ethylene methoxycarbonylation (EMC) reaction in the absence of acid promoter. The catalyst offers 92% yield of MP with TOF of 8666 h–1, which is about 2.5 times of homogeneous Pd catalyst (∼3500 h–1). The interfacial Lewis acid–base pair [Ru-O-Ce-Vo], which consists of acidic Ce-Vo (oxygen vacancy) site and basic interfacial oxygen of Ru-O-Ce linkage, acts as active site for the dissociation of methanol and the subsequent transfer of hydrogen to the activated ethylene, which is the key step in acid-promoter-free EMC reaction. The combination of 1H MAS NMR, pyridine-IR and DFT calculations reveals the hydrogen species derived from methanol contains Bronsted acidity. The EMC reaction mechanism under acid-promoter-free condition over Ru-clusters/ceria catalyst is discussed.

Selective Hydrogen Atom Abstraction through Induced Bond Polarization: Direct α-Arylation of Alcohols through Photoredox, HAT, and Nickel Catalysis

Abstract: The combination of nickel metallaphotoredox catalysis, hydrogen atom transfer catalysis, and a Lewis acid activation mode, has led to the development of an arylation method for the selective functionalization of alcohol α-hydroxy C-H bonds. This approach employs zinc-mediated alcohol deprotonation to activate α-hydroxy C-H bonds while simultaneously suppressing C-O bond formation by inhibiting the formation of nickel alkoxide species. The use of Zn-based Lewis acids also deactivates other hydridic bonds such as α-amino and α-oxy C-H bonds. This approach facilitates rapid access to benzylic alcohols, an important motif in drug discovery. A 3-step synthesis of the drug Prozac exemplifies the utility of this new method.

Remarkable Enhancement of the Hole Mobility in Several Organic Small-Molecules, Polymers, and Small-Molecule:Polymer Blend Transistors by Simple Admixing of the Lewis Acid p-Dopant B(C6F5)3.

Abstract: Improving the charge carrier mobility of solution-processable organic semiconductors is critical for the development of advanced organic thin-film transistors and their application in the emerging sector of printed electronics. Here, a simple method is reported for enhancing the hole mobility in a wide range of organic semiconductors, including small-molecules, polymers, and small-molecule:polymer blends, with the latter systems exhibiting the highest mobility. The method is simple and relies on admixing of the molecular Lewis acid B(C6F5)3 in the semiconductor formulation prior to solution deposition. Two prototypical semiconductors where B(C6F5)3 is shown to have a remarkable impact are the blends of 2,8-difluoro-5,11-bis(triethylsilylethynyl)anthradithiophene:poly(triarylamine) (diF-TESADT:PTAA) and 2,7-dioctyl[1]-benzothieno[3,2-b][1]benzothiophene:poly(indacenodithiophene-co-benzothiadiazole) (C8-BTBT:C16-IDTBT), for which hole mobilities of 8 and 11 cm2 V-1 s-1, respectively, are obtained. Doping of the 6,13-bis(triisopropylsilylethynyl)pentacene:PTAA blend with B(C6F5)3 is also shown to increase the maximum hole mobility to 3.7 cm2 V-1 s-1. Analysis of the single and multicomponent materials reveals that B(C6F5)3 plays a dual role, first acting as an efficient p-dopant, and secondly as a microstructure modifier. Semiconductors that undergo simultaneous p-doping and dopant-induced long-range crystallization are found to consistently outperform transistors based on the pristine materials. Our work underscores Lewis acid doping as a generic strategy towards high performance printed organic microelectronics.

Honeycomb Metal–Organic Framework with Lewis Acidic and Basic Bifunctional Sites: Selective Adsorption and CO2 Catalytic Fixation

Abstract: Carrying out the strategy of incorporating rod secondary building units and polar functional groups in metal–organic frameworks (MOFs) to accomplish the separation of CO2 and C2 hydrocarbons over CH4 as well as CO2 fixation, an oxalamide-functionalized ligand N,N′-bis(isophthalic acid)-oxalamide (H4BDPO) has been designed. The solvothermal reaction of H4BDPO with the oxophilic alkaline-earth Ba2+ ion afforded a honeycomb Ba-MOF, {[Ba2(BDPO)(H2O)]·DMA}n (1). Due to the existence of Lewis basic oxalamide groups and unsaturated Lewis acid metal sites in the tubular channels, the activated framework presents not only high C2H6, C2H4, and CO2 uptakes and selective capture from CH4, but also efficient CO2 chemical fixation as a recyclable heterogeneous catalyst. Grand canonical Monte Carlo simulations were combined to explore the adsorption selectivities for C2H6–CH4 and C2H4–CH4 mixtures as well as the interaction mechanisms between the framework and epoxides.

Pd-Catalyzed Enantioselective [6+4] Cycloaddition of Vinyl Oxetanes with Azadienes to Access Ten-Membered Heterocycles.

Abstract: We report herein the first enantioselective cycloaddition of vinyl oxetanes, the reaction of which with azadienes provided unprecedented access to ten-membered heterocycles through a [6+4] cycloaddition. By using a commercially available chiral Pd-SIPHOX catalyst, a wide range of benzofuran- as well as indole-fused heterocycles could be accessed in excellent yield and enantioselectivity. A unique Lewis acid induced fragmentation of these ten-membered heterocycles was also discovered.

Mechanisms in Iodine Catalysis.

Abstract: Molecular iodine has been used for more than 100 years as a remarkable catalyst for many organic transformations such as cycloadditions, Michael and aldol reactions, or esterifications. Different explanations for the origin of its catalytic effect have been proposed in the last decades including a "hidden" Bronsted acid catalysis by HI, a Lewis-acid (or halogen-bond) activation, or catalysis by an iodonium(I) species. Recently, iodine catalysis again gained more interest due to the latest developments in halogen-bond catalysis. In this Minireview, we first summarize the experimental basis for the proposed modes of activation. Subsequently, we analyze typical iodine-catalyzed reactions to gain more insights into the underlying reaction mechanisms.

Brønsted-Acid-Catalyzed Exchange in Polyester Dynamic Covalent Networks

Abstract: The effect of catalyst strength on polyester–alcohol dynamic covalent exchange was systematically studied using Bronsted acids and a low-Tg poly(4-methylcaprolactone) vitrimer formulation. Relaxation times, activation energies, and Arrhenius prefactors are correlated with pKa. Strong protic acids induce facile network relaxation at 25 °C on the order of 104–105 s, significantly faster than Lewis acid alternatives that function only above 100 °C. Activation energies span 49–67 kJ/mol and increase as pKa decreases. The opposite trend is observed with the Arrhenius prefactor. We anticipate that the quantitative understanding of Bronsted acid effects disclosed herein will be of utility in future studies that exploit acid-catalyzed dynamic covalent bond exchange.

Strategies to Explore and Develop Reversible Redox Reactions of Li-S in Electrode Architectures Using Silver-Polyoxometalate Clusters.

Abstract: Investigations of the Ag (I)-substituted Keggin K3[H3AgIPW11O39] as a bifunctional Lewis acidic and basic catalyst are reported that explore the stabilization of Li2Sn moieties so that reversible redox reactions in S-based electrodes would be possible. Spectroscopic investigations showed that the Li2Sn-moieties can be strongly adsorbed on the {AgIPW11O39} cluster, where the Ag(I) ion can act as a Lewis acid site to further enhance the adsorption of the S-moieties, and these interactions were investigated and rationalized using DFT. These results were used to construct an electrode for use in a Li-S battery with a very high S utilization of 94%, and a coulometric capacity of 1580 mAh g-1. This means, as a result of using the AgPOM, both a high active S content, as well as a high areal S mass loading, is achieved in the composite electrode giving a highly stable battery with cycling performance at high rates (1050 and 810 mAh g-1 at 1C and 2C over 100 to 300 cycles, respectively).

Picking One out of Three: Selective Single C−F Activation in Trifluoromethyl Groups

Abstract: The introduction of a trifluoromethyl (CF3 ) group into an organic molecule can modify its chemical behavior and lead to changes in its physicochemical and pharmacological properties. The CF3 group is often chosen for its chemical inertness and stability, which are related to the strong C-F bonds. In recent years, the potential of gaining straightforward access to difluorinated compounds through selective single C-F activation in CF3 groups has been unveiled. This review describes the latest methodologies for the synthesis of difluoromethylated arenes, difluoroalkenes and difluorinated aldol products of potential synthetic and/or biological interest, employing low-valent metals, transition metal catalysis, FLP and Lewis acid mediated transformations as well as photoredox catalysis.

Origin and Structural Characteristics of Tri-coordinated Extra-framework Aluminum Species in Dealuminated Zeolites.

Abstract: Post-synthetic dealumination treatment is a common tactic adopted to improve the catalytic performance of industrialized zeolitic catalysts through enhancements in acidity and stability. However, among the possible extra-framework aluminum (EFAL) species in dealuminated zeolites such as Al3+, Al(OH)2+, Al(OH)2+, AlO+, AlOOH, and Al(OH)3, the presence of tri-coordinated EFAL-Al3+ species, which exhibit large quadrupolar effect due to the lack of hydrogen-bonding species, was normally undetectable by conventional one- and two-dimensional 1H and/or 27Al solid-state nuclear magnetic resonance (SSNMR) techniques. By combining density functional theory (DFT) calculations with experimental 31P SSNMR using trimethylphosphine (TMP) as the probe molecule, we report herein a comprehensive study to certify the origin, fine structure, and possible location of tri-coordinated EFAL-Al3+ species in dealuminated HY zeolite. The spatial proximities and synergies between the Bronsted and various Lewis acid sites were clearl...

Novel 3D Nitrogen-Rich Metal Organic Framework for Highly Efficient CO2 Adsorption and Catalytic Conversion to Cyclic Carbonates under Ambient Temperature

Abstract: A novel Lewis acid–base bifunctional Zn(II)-based MOF-Zn-1 [Zn2L2MA·2DMF] (MA = melamine, H2L = 2,5-thiophenedicarboxylic acid), with abundant micropores and free -NH2 groups was facilely assembled...

Brønsted/Lewis Acid Synergy in Methanol-to-Aromatics Conversion on Ga-Modified ZSM-5 Zeolites, As Studied by Solid-State NMR Spectroscopy

Abstract: 1H–71Ga internuclear spatial proximity/interaction between Bronsted acid site (BAS) and cationic Ga species (Lewis acid sites) in Ga-modified ZSM-5 zeolites, which leads to a synergic effect in the methanol-to-aromatics (MTA) conversion, was identified with solid-state NMR spectroscopy. The internuclear distance between BAS and Ga species was measured, which is similar to that of a neighboring BAS pair located in the six-membered rings of ZSM-5. The Bronsted acidity of the Ga-modified zeolite was considerably enhanced due to the synergic effect, and the synergic active sites were quantified by 1H–71Ga double-resonance solid-state NMR, which shows a correlation with the aromatics selectivity in the MTA reaction.