Dong-Dong Zhou  Jun Wang  Pin Chen  Yangyong He  Jun-Xi Wu  Sen Gao  Zhihao Zhong  Yunfei Du  Dingyong Zhong  Jie-Peng Zhang 《Chemical science》2021,12(4):1272

Rational manipulation of supramolecular structures on surfaces is of great importance and challenging. We show that imidazole-based hydrogen-bonded networks on a metal surface can transform into an isostructural coordination network for facile tuning of the pore size and guest recognition behaviours. Deposition of triangular-shaped benzotrisimidazole (H₃btim) molecules on Au(111)/Ag(111) surfaces gives honeycomb networks linked by double N–H⋯N hydrogen bonds. While the H₃btim hydrogen-bonded networks on Au(111) evaporate above 453 K, those on Ag(111) transform into isostructural [Ag₃(btim)] coordination networks based on double N–Ag–N bonds at 423 K, by virtue of the unconventional metal–acid replacement reaction (Ag reduces H⁺). The transformation expands the pore diameter of the honeycomb networks from 3.8 Å to 6.9 Å, giving remarkably different host–guest recognition behaviours for fullerene and ferrocene molecules based on the size compatibility mechanism.

A hydrogen-bonded network on a Ag(111) surface can transform into an isostructural Ag(i) coordination network, giving drastically different host–guest recognition behaviours.  相似文献   

    

Xiao-Long Lu  Yuanyou Qiu  Baochao Yang  Haibing He  Shuanhu Gao 《Chemical science》2021,12(13):4747

The asymmetric total synthesis of (+)-xestoquinone and (+)-adociaquinones A and B was achieved in 6–7 steps using an easily accessible meso-cyclohexadienone derivative. The [6,6]-bicyclic decalin B–C ring and the all-carbon quaternary stereocenter at C-6 were prepared via a desymmetric intramolecular Michael reaction with up to 97% ee. The naphthalene diol D–E ring was constructed through a sequence of Ti(Oi-Pr)₄-promoted photoenolization/Diels–Alder, dehydration, and aromatization reactions. This asymmetric strategy provides a scalable route to prepare target molecules and their derivatives for further biological studies.

The asymmetric total synthesis of (+)-xestoquinone and (+)-adociaquinones A and B was achieved in 6–7 steps using an easily accessible meso-cyclohexadienone derivative.

Various halenaquinone-type natural products with promising biological activity have been isolated from marine sponges of the genus Xestospongia¹ from the Pacific Ocean. (+)-Halenaquinone (1),^2,3 (+)-xestoquinone (2), and (+)-adociaquinones A (3) and B (4)^4,5 bearing a naphtha[1,8-bc]furan core (Fig. 1) are the most typical representatives of this family. Naturally occurring (−)-xestosaprol N (5) and O (6)^6,7 have the same structure as 3 and 4 except for a furan ring, while a naphtha[1,8-bc]furan core can also be found in fungus-isolated furanosteroids (−)-viridin (7) and (+)-nodulisporiviridin E (8)^8,9 (Fig. 1). Halenaquinone (1) was first isolated from the tropical marine sponge Xestospongia exigua² and it shows antibiotic activity against Staphylococcus aureus and Bacillus subtilis. Xestoquinone (2) and adociaquinones A (3) and B (4) were firstly isolated, respectively, from the Okinawan marine sponge Xestospongia sp.^4a and the Truk Lagoon sponge Adocia sp.,^4b and they show cardiotonic,^4a,c cytotoxic,^4b,i antifungal,⁴ⁱ antimalarial,^4j and antitumor^4l activities. These compounds inhibit the activity of pp60v-src protein tyrosine kinase,^4d topoisomerases I^4e and II,^4f myosin Ca²⁺ ATPase,^4c,g and phosphatases Cdc25B, MKP-1, and MKP-3.^4h,kOpen in a separate windowFig. 1Structure of halenaquinone-type natural products and viridin-type furanosteroids.Owing to their diverse bioactivities, the synthesis of this family of natural compounds has been extensively studied, with published pathways making use of Diels–Alder,^{3a,d,e,5a–c,e,g} furan ring transfer,^5b Heck,^{3b,c,5f,7,9b,d} palladium-catalyzed polyene cyclization,^5d Pd-catalyzed oxidative cyclization,^3f and hydrogen atom transfer (HAT) radical cyclization^9c reactions. In this study, we report the asymmetric total synthesis of (+)-xestoquinone (2), (−)-xestoquinone (2′), and (+)-adociaquinones A (3) and B (4) (Fig. 1).The construction of the fused tetracyclic B–C–D–E skeleton and the all carbon quaternary stereocenter at C-6 is a major challenge towards the total synthesis of xestoquinone (2) and adociaquinones A (3) and B (4). Based on our retrosynthetic analysis (Scheme 1), the all-carbon quaternary carbon center at C-6 of cis-decalin 12 could first be prepared stereoselectively from the achiral aldehyde 13via an organocatalytic desymmetric intramolecular Michael reaction.^10,11 The tetracyclic framework 10 could then be formed via a Ti(Oi-Pr)₄-promoted photoenolization/Diels–Alder (PEDA) reaction^12–16 of 11 and enone 12. Acid-mediated cyclization of 10 followed by oxidation state adjustment could be subsequently applied to form the furan ring A of xestoquinone (2). Finally, based on the biosynthetic pathway of (+)-xestoquinone (2)^4b,5c and our previous studies,⁷ the heterocyclic ring F of adociaquinones A (3) and B (4) could be prepared from 2via a late-stage cyclization with hypotaurine (9).Open in a separate windowScheme 1Retrosynthetic analysis of (+)-xestoquinone and (+)-adociaquinones A and B.The catalytic enantioselective desymmetrization of meso compounds has been used as a powerful strategy to generate enantioenriched molecules bearing all-carbon quaternary stereocenters.^10,11 For instance, two types of asymmetric intramolecular Michael reactions were developed using a cysteine-derived chiral amine as an organocatalyst by Hayashi and co-workers,^11a,b while a desymmetrizing secondary amine-catalyzed asymmetric intramolecular Michael addition was later reported by Gaunt and co-workers to produce enantioenriched decalin structures.^11c Prompted by these pioneering studies and following the suggested retrosynthetic pathway (Scheme 1), we first screened conditions for organocatalytic desymmetric intramolecular Michael addition of meso-cyclohexadienone 13 (Table 1) in order to form the desired quaternary stereocenter at C-6. Compound 13 was easily prepared on a gram scale via a four-step process (see details in the ESI^†).Attempts of organocatalytic desymmetric intramolecular Michael addition^a

Entry	Cat. (equiv.)	Additive (equiv.)	Solvent	Time	Yield/d.r. at C2b	e.e.c
1	(R)-cat.I (0.5)	—	Toluene	10.0 h	52%/10.3 : 1	14a: 96%; 14b: 75%
2	(R)-cat.I (1.0)	—	Toluene	4.0 h	60%/10.0 : 1	14a: 93%; 14b: 75%
3	(R)-cat.I (1.0)	—	MeOH	4.0 h	47%/5.5 : 1	14a: 86%; 14b: −3%
4	(R)-cat.I (1.0)	—	DCM	10.0 h	28%/24.0 : 1	14a: 91%; 14b: 7%
5	(R)-cat.I (1.0)	—	Et2O	10.0 h	22%/22.0 : 1	14a: 91%; 14b: 65%
6	(R)-cat.I (1.0)	—	MeCN	10.0 h	12%/2.6 : 1	14a: 90%; 14b: 62%
7	(R)-cat.I (1.0)	—	Toluene/MeOH (2 : 1)	4.0 h	47%/10.0 : 1	14a: 87%; 14b: −38%
8d	(R)-cat.I (1.0)	AcOH (5.0)	Toluene	4.0 h	60%e/2.1 : 1	14a: 96%; 14b: 95%
9d	(R)-cat.I (0.5)	AcOH (2.0)	Toluene	6.0 h	75%e/4.0 : 1	14a: 97%; 14b: 91%
10d	(R)-cat.I (0.5)	AcOH (0.2)	Toluene	6.0 h	73%e/4.3 : 1	14a: 96%; 14b: 92%
11f	(R)-cat.I (0.5)	AcOH (0.2)	Toluene	6.0 h	75%e/8.0 : 1g	14a: 95%; 14b: 93%
12h	(R)-cat.I (0.2)	AcOH (0.2)	Toluene	9.0 h	80%i/6.0 : 1j	14a: 97%; 14b: 91%

Open in a separate window^aAll reactions were performed using 13 (5.8 mg, 0.03 mmol, 1.0 equiv., and 0.1 M) and a catalyst at room temperature in analytical-grade solvents, unless otherwise noted.^bThe yields and diastereoisomeric ratios (d.r.) were determined from the crude ¹H NMR spectrum of 14 using CH₂Br₂ as an internal standard, unless otherwise noted.^cThe enantiomeric excess (e.e.) values were determined by chiral high-performance liquid chromatography (Chiralpak IG-H).^dCompound 13: 9.6 mg, 0.05 mmol, and 0.1 M.^eIsolated combined yield of 14a + 14b.^fCompound 13: 192 mg, 1.0 mmol, and 0.1 M.^gThe d.r. values decreased to 1 : 1 after purification by silica gel column chromatography.^hCompound 13: 1.31 g, 6.82 mmol, and 0.1 M.ⁱIsolated combined yield of 12a + 12b.^jThe d.r. values were determined from the crude ¹H NMR spectrum of 12 obtained from the one-pot process.We initially investigated the desymmetric intramolecular Michael addition of 13 using (S)-Hayashi–Jørgensen catalysts,¹⁷ and found that the absolute configuration of the obtained cis-decalin was opposite to the required stereochemistry of the natural products (see Table S1 in the ESI^†). In order to achieve the desired absolute configuration of the angular methyl group at C-6, (R)-cat.I was used for further screening. In the presence of this catalyst, the intramolecular Michael addition afforded 14a (96% e.e.) and 14b (75% e.e.) in a ratio of 10.3 : 1 and 52% combined yield (entry 1, Table 1). We assumed that the enantioselectivity of the reaction was controlled by the more sterically hindered aromatic group of (R)-cat.I, which protected the upper enamine face and allowed an endo-like attack by the si-face of cyclohexadienone, as shown in the transition state TS-A (Table 1). In order to increase the yield of this reaction and improve the enantioselectivity of 14b, we further screened solvents and additives. Increasing the catalyst loading from 0.5 to 1.0 equivalents and screening various reaction solvents did not improve the enantiomeric excess of 14b (entries 2–7, Table 1). Therefore, based on previous studies,^11d,e we added 5.0 equivalents of acetic acid (AcOH) to a solution of compound 13 and (R)-cat.I in toluene, which improved the enantiomeric excess of 14b to 95% with a 60% combined yield (entry 8, Table 1). And, the stability of (R)-cat.I has also been verified in the presence of AcOH (see Table S2 in the ESI^†). Further adjustment of the (R)-cat.I and AcOH amount and ratio (entries 9–12, Table 1) indicated that 0.2 equivalents each of (R)-cat.I and AcOH were the best conditions to achieve high enantioselectivity for both 14a and 14b, and it also increased the reaction yield (entry 12, Table 1). The enantioselectivity was not affected when the optimized reaction was performed on a gram scale: 14a (97% e.e.) and 14b (91% e.e.) were obtained in 80% isolated yield (entry 12, Table 1). We also found that the gram-scale experiments needed a longer reaction time which led a slight decrease of the diastereoselectivity. The purification of the cyclized products by silica gel flash column chromatography indicated that the major product 14a was epimerized and slowly converted to the minor product 14b (entry 11, Table 1). Both 14a and 14b are useful in the syntheses because the stereogenic center at C-2 will be converted to sp² hybridized carbon in the following transformations. Therefore, the aldehyde group of analogues 14a and 14b was directly protected with 1,3-propanediol to give the respective enones 12a and 12b for use in the subsequent PEDA reaction.Afterward, we selected the major cyclized cis-decalins 12a and 12a′ (obtained by using (S)-cat.I in desymmetric intramolecular Michael addition, see Table S1 in the ESI^†) as the dienophiles to prepare the tetracyclic naphthalene framework 10 through a sequence of Ti(Oi-Pr)₄-promoted PEDA, dehydration, and aromatization reactions (Scheme 2). When using 3,6-dimethoxy-2-methylbenzaldehyde (11) as the precursor of diene, no reaction occurred between 12a/12a′ and 11 under UV irradiation at 366 nm in the absence of Ti(Oi-Pr)₄ (Scheme 2A). In contrast, the 1,2-dihydronaphthalene compounds 16a and 16a′ were successfully synthesized when 3.0 equivalents of Ti(Oi-Pr)₄ were used. Based on our previous studies,^13a,e the desired hydroanthracenol 15a was probably generated through the chelated intermediate TS-B and the cycloaddition occurred through an endo direction (Scheme 2B).¹⁸ The newly formed β-hydroxyl ketone groups in 15a and 15a′ could then be dehydrated with excess Ti(Oi-Pr)₄ to form enones 16a and 16a′. These results confirmed the pivotal role of Ti(Oi-Pr)₄ in this PEDA reaction: it stabilized the photoenolized hydroxy-o-quinodimethanes and controlled the diastereoselectivity of the reaction.Open in a separate windowScheme 2PEDA reaction of 11 and enone 12.Subsequent aromatization of compounds 16a and 16a′ with 2,3-dichloro-5,6-dicyanobenzoquinone (DDQ) at 80 °C afforded compounds 10a and 10a′ bearing a fused tetracyclic B–C–D–E skeleton. The stereochemistry and absolute configuration of 10a were confirmed by X-ray diffraction analysis of single crystals (Scheme 3). The synthesis of (+)-xestoquinone (2) and (+)-adociaquinones A (3) and B (4) was completed by forming the furan A ring. Compound 10 was oxidized using bubbling oxygen gas in the presence of t-BuOK to give the unstable diosphenol 17a, which was used without purification in the next step. The subsequent acid-promoted deprotection of the acetal group led to the formation of an aldehyde group, which reacted in situ with enol to furnish the pentacyclic compound 18 bearing the furan A ring. The stereochemistry and absolute configuration of 18 were confirmed by X-ray diffraction analysis of single crystals (Scheme 3). Further oxidation of 18 with ceric ammonium nitrate afforded (+)-xestoquinone (2) in 82% yield. Following the same reaction process, (−)-xestoquinone (2′) was also synthesized from 10a′ in order to determine in the future whether xestoquinone enantiomers differ in biological activity. Further heating of a solution of (+)-xestoquinone (2) with hypotaurine (9) at 50 °C afforded a mixture of (+)-adociaquinones A (3) (21% yield) and B (4) (63% yield). We also tried to optimize the selectivity of this condensation by tuning the reaction temperature and pH of reaction mixtures (see Table S3 in the ESI^†). The ¹H and ¹³C NMR spectra, high-resolution mass spectrum, and optical rotation of synthetic (+)-xestoquinone (2), (+)-adociaquinones A (3) and B (4) were consistent with those data reported by Nakamura,^4a,g Laurent,^4j Schmitz,^4b Harada^5a,c and Keay.^5dOpen in a separate windowScheme 3Total synthesis of (+)-xestoquinone and (+)-adociaquinones A and B.  相似文献   

    

Yulong Bai  Wang Wan  Yanan Huang  Wenhan Jin  Haochen Lyu  Qiuxuan Xia  Xuepeng Dong  Zhenming Gao  Yu Liu 《Chemical science》2021,12(24):8468

Co-aggregation of multiple pathogenic proteins is common in neurodegenerative diseases but deconvolution of such biochemical process is challenging. Herein, we developed a dual-color fluorogenic thermal shift assay to simultaneously report on the aggregation of two different proteins and quantitatively study their thermodynamic stability during co-aggregation. Expansion of spectral coverage was first achieved by developing multi-color fluorogenic protein aggregation sensors. Orthogonal detection was enabled by conjugating sensors of minimal fluorescence crosstalk to two different proteins via sortase-tag technology. Using this assay, we quantified shifts in melting temperatures in a heterozygous model protein system, revealing that the thermodynamic stability of wild-type proteins was significantly compromised by the mutant ones but not vice versa. We also examined how small molecule ligands selectively and differentially interfere with such interplay. Finally, we demonstrated these sensors are suited to visualize how different proteins exert influence on each other upon their co-aggregation in live cells.

A little leak will sink a great ship! We prepared a series of multi-color protein aggregation sensors and developed a dual-color thermal shift assay to simultaneously and quantitatively report on protein co-aggregation of two different proteins.  相似文献   

    

Yang Wang  Weizhe Gao  Kangzhou Wang  Xinhua Gao  Baizhang Zhang  Heng Zhao  Qingxiang Ma  Peipei Zhang  Guohui Yang  Mingbo Wu  Noritatsu Tsubaki 《Chemical science》2021,12(22):7786

Even though the transformation of syngas into aromatics has been realized via a methanol-mediated tandem process, the low product yield is still the bottleneck, limiting the industrial application of this technology. Herein, a tailor-made zeolite capsule catalyst with Ga doping and SiO₂ coating was combined with the methanol synthesis catalyst Cr₂O₃ to boost the synthesis of value-added aromatics, especially para-xylene, from syngas. Multiple characterization studies, control experiments, and density functional theory (DFT) calculation results clarified that Ga doped zeolites with strong CO adsorption capability facilitated the transformation of the reaction intermediate methanol by optimizing the first C–C coupling step under a high-pressure CO atmosphere, thereby driving the reaction forward for aromatics synthesis. This work not only reveals the synergistic catalytic network in the tandem process but also sheds new light on principles for the rational design of a catalyst in terms of oriented conversion of syngas.

The single-pass conversion of syngas into para-xylene was realized using a bifunctional catalyst Cr₂O₃/Ga-ZSM-5@SiO₂. The Ga species facilitates the methanol consumption process by C–C coupling optimization, enhancing the yield of the target aromatics.  相似文献   

    

Zhao Gao  Shuai Qiu  Fei Yan  Shuyi Zhang  Feng Wang  Wei Tian 《Chemical science》2021,12(29):10041

Innovative fluorescence security technologies for paper-based information are still highly pursued nowadays because data leakage and indelibility have become serious economic and social problems. Herein, we report a novel transient bio-fluorochromic supramolecular co-assembly mediated by a hydrolytic enzyme (ALP: alkaline phosphatase) towards rewritable security printing. A co-assembly based on the designed tetrabranched cationic diethynylanthracene monomer tends to be formed by adding adenosine triphosphate (ATP) as the biofuel. The resulting co-assembly possesses a time-encoded bio-fluorochromic feature, upon successively hydrolyzing ATP with ALP and re-adding new batches of ATP. On this basis, the dynamic fluorescent properties of this time-encoded co-assembly system have been successfully enabled in rewritable security patterns via an inkjet printing technique, providing fascinating potential for fluorescence security materials with a biomimetic mode.

Rewritable security printing has been successfully achieved based on a biofuel-driven transient supramolecular co-assembly mediated by an enzyme, providing fascinating potential for artificial functional materials with a biomimetic mode.  相似文献   

    

Na Yang  Lanlan Peng  Li Li  Jing Li  Qiang Liao  Minhua Shao  Zidong Wei 《Chemical science》2021,12(37):12476

For the FeNC catalyst widely used in the oxygen reduction reaction (ORR), its instability under fuel cell (FC) operating conditions has become the biggest obstacle during its practical application. The complexity of the degradation process of the FeNC catalyst in FCs poses a huge challenge when it comes to revealing the underlying degradation mechanism that directly leads to the decay in ORR activity. Herein, using density functional theory (DFT) and ab initio molecular dynamics (AIMD) approaches and the FeN₄ moiety as an active site, we find that during catalyzing the ORR, Fe site oxidation in the form of *Fe(OH)₂, in which 2OH* species are adsorbed on Fe on the same side of the FeN₄ plane, results in the successive protonation of N and then permanent damage to the FeN₄ moiety, which causes the leaching of the Fe site in the form of Fe(OH)₂ species and a sharp irreversible decline in the ORR activity. However, other types of OH* adsorption on Fe in the form of HO*FeOH and *FeOH intermediates cannot cause the protonation of N or any breaking of Fe–N bonds in the FeN₄ moiety, only inducing the blocking of the Fe site. Meanwhile, based on the competitive relationship between catalyzing the ORR and Fe site oxidation, we propose a trade-off potential (U^RHE_TMOR) to describe the anti-oxidation abilities of the TM site in the TMN_X moiety during the ORR.

We summarize possible catalyst degradation mechanisms during the ORR. Protonation on an N atom of bare FeNC catalysts is difficult, leaching of the Fe site is also likely to happen, due to successive N protonation that destroys the FeN₄ moiety releasing Fe(OH)₂ species.  相似文献   

    

Hao Zhang  Ze Gao  Xiaoxiao Li  Lu Li  Sujuan Ye  Bo Tang 《Chemical science》2021,12(37):12429

Multifunctional drug delivery systems enabling effective drug delivery and comprehensive treatment are critical to successful cancer treatment. Overcoming nonspecific release and off-target effects remains challenging in precise drug delivery. Here, we design triple-interlocked drug delivery systems to perform specific cancer cell recognition, controlled drug release and effective comprehensive therapy. Gold nanocages (AuNCs) comprise a novel class of nanostructures possessing hollow interiors and porous walls. AuNCs are employed as a drug carrier and photothermal transducer due to their unique structure and photothermal properties. A smart triple-interlocked I-type DNA nanostructure is modified on the surface of the AuNCs, and molecules of the anticancer drug doxorubicin (DOX) are loaded as molecular cargo and blocked. The triple-interlocked nanostructure can be unlocked by binding with three types of tumor-related mRNAs, which act as “keys” to the triple locks, sequentially, which leads to precise drug release. Additionally, fluorescence-imaging-oriented chemical–photothermal synergistic treatment is achieved under illumination with infrared light. This drug delivery system, which combines the advantages of AuNCs and interlocked I-type DNA, successfully demonstrates effective and precise imaging, drug release and photothermal therapy. This multifunctional triple-interlocked drug delivery system could be used as a potential carrier for effective cancer-targeting comprehensive chemotherapy and photothermal therapy treatments.

Schematic illustration of the multiple-mRNA-controlled and heat-driven drug release from gold nanocages.  相似文献   

    

Cong Ma  Ping Fang  Dong Liu  Ke-Jin Jiao  Pei-Sen Gao  Hui Qiu  Tian-Sheng Mei 《Chemical science》2021,12(39):12866

Transition metal-catalyzed organic electrochemistry is a rapidly growing research area owing in part to the ability of metal catalysts to alter the selectivity of a given transformation. This conversion mainly focuses on transition metal-catalyzed anodic oxidation and cathodic reduction and great progress has been achieved in both areas. Typically, only one of the half-cell reactions is involved in the organic reaction while a sacrificial reaction occurs at the counter electrode, which is inherently wasteful since one electrode is not being used productively. Recently, transition metal-catalyzed paired electrolysis that makes use of both anodic oxidation and cathodic reduction has attracted much attention. This perspective highlights the recent progress of each type of electrochemical reaction and relatively focuses on the transition metal-catalyzed paired electrolysis, showcasing that electrochemical reactions involving transition metal catalysis have advantages over conventional reactions in terms of controlling the reaction activity and selectivity and figuring out that transition metal-catalyzed paired electrolysis is an important direction of organic electrochemistry in the future and offers numerous opportunities for new and improved organic reaction methods.

Transition metal-catalyzed organic electrochemistry is a rapidly growing research area owing in part to the ability of metal catalysts to alter the selectivity of a given transformation.  相似文献   

    

Wange Song  Yuxin Chen  Hanmeng Li  Shenglun Gao  Shengjie Wu  Chen Chen  Shining Zhu  Tao Li 《Laser u0026amp; Photonics Reviews》2021,15(8):2000584

Tremendous efforts are devoted to the research of exotic photonic topological states, in which Floquet systems suggest new engineered topological phases and provide a powerful tool to manipulate the optical fields. Here, a gauge-induced topological state localized at the interface between two gauge-shifted Floquet photonic lattices with the same topological order is demonstrated. The quasienergy band structures reveal that these interface modes belong to the Floquet π modes, which are further found to enable an asymmetric topological transport of this interface mode thanks to the flexible control of the Floquet gauge. The intriguing propagations of the gauge-induced topological states are experimentally verified in a silicon waveguides platform at near-infrared wavelengths, which show broadband working wavelengths and robustness against the structural fluctuations. This work provides a new route in manipulating optical topological modes by Floquet engineering and inspires more possibilities in photonics integrations.  相似文献   

    

Xiaoming Su  Linyuan Lian  Chi Zhang  Jianbing Zhang  Sisi Liu  Sheng Zhu  Yulong Gao  Wei Luo  Honglang Li  Daoli Zhang 《Advanced Optical Materials》2021,9(15):2001866

Lead-free halide double perovskite Cs₂AgInCl₆ has attracted great attention due to its highly efficient luminescence and excellent stability. However, the parity forbidden electronic transition limits further applications in lighting and display fields. In this work, Cs₂AgInCl₆ nanocrystals (NCs) are synthesized by injecting trimethyl chlorosilane into the dissolved precursors at 180 °C and the as-synthesized Cs₂AgInCl₆ NCs exhibit a weak orange emission peak at 570 nm with a photoluminescence quantum yield (PLQY) of 1.5%. In order to break the parity forbidden transition, various amounts of Na are alloyed into Cs₂AgInCl₆ NCs, resulting a peak PLQY of 13.4% in Cs₂Na_0.6Ag_0.4InCl₆ NCs. Then Mn²⁺ doped Cs₂Na_xAg_1−xInCl₆ NCs are synthesized in the same approach, in which the highest PLQY can be enhanced up to 36%. As a result, a redshifted photoluminescence emission peak at 625 nm is observed, which derives from the ⁴T₁→⁶A₁ transition of Mn²⁺ that is related to the ultrafast energy transfer from self-trapped exciton states to the ⁴T₁ excited state of Mn²⁺.  相似文献