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Nickel-catalyzed cross-coupling of allyl alcohols with aryl- and alkenylzinc chlorides through C-O bond cleavage was performed. Reaction of (E)-3-phenylprop-2-en-1-ol and 1-aryl-prop-2-en-1-ols with aryl- or alkenylzinc chlorides gave linear cross-coupling products. Reaction of 1-phenyl- or 1-methyl-substituted (E)-3-phenylprop-2-en-1-ol with aryl- or alkenylzinc chlorides resulted in 3-aryl/alkenyl-substituted (E)-(prop-1-ene-1,3-diyl)dibenzenes or 3-aryl/alkenyl-substituted (E)-(but-1-enyl)benzene. Reaction of allyl alcohol with p-Me2NC6H4ZnCl resulted in a mixture of normal coupling product 4-allyl-N,N-dimethylaniline and its isomerized product N,N-dimethyl-4-(prop-1-en-1-yl)aniline. [ABSTRACT FROM AUTHOR]

Research into the synthesis and structural characterization of a series of low-valent group 14 1,3-dimetallacyclobutanes and an unusual 1,3-stanna-plumbacyclobutane is presented. It was found that lithium iminophosporano(pyridyl)methanide complex reacts with MCl2 (M = Ge, Sn, Pb) to produce unusual low-valent group 14 1,3-dimetallacyclobutanes.

Condensationof 2-NH2C6H4P(Et)Ph(2) with pyrrole-2-carboxaldehyde generated 2-(C4H4N-2′-CHN)C6H4P(Et)Ph (3). Treatment of 3with NaH andfollowed by (DME)NiX2(X = Cl, Br) afforded mononuclearpincer nickel complexes [Ni{2-(C4H3N-2′-CHN)C6H4P(Et)Ph}X] (4a, X = Cl; 4b, X = Br). Reaction of [2-NH2C6H4P(Ph)]2(CH2)n(5a, n= 3; 5b, n= 4) with pyrrole-2-carboxaldehyde or 5-tert-butyl-1H-pyrrole-2-carbaldehyde formed [2-(C4H4N-2′-CHN)C6H4P(Ph)]2(CH2)n(6a, n= 3; 6b, n= 4) and [2-(5′-tBuC4H3N-2′-CHN)C6H4P(Ph)]2(CH2)4(6c). Respective treatment of 6a–cwith NaH followed by (DME)NiX2(X = Cl, Br) gavethe dinuclear nickel complexes [Ni{2-(5′-RC4H2N-2′-CHN)C6H4P(Ph)}X]2(CH2)n(7a, R = H, X = Cl, n= 3; 7b, R = H,X = Cl, n= 4; 7c, R = H, X = Br, n= 4; 7d, R = tBu, X = Cl, n= 4). Catalysis of the complexes for the activation andtransformation of C–Cl, C–N, and C–O bonds wasevaluated. Complex 7cexhibited excellent catalytic activityin the cross-coupling of aryl chlorides or aryltrimethylammonium iodideswith arylzinc reagents as well as of aryl sulfamates with aryl Grignardreagents. The dinuclear nickel complexes 7b–dshowed higher catalytic activity than the mononuclear complexesin each type of reaction. [ABSTRACT FROM AUTHOR]

Organic photochromic compounds have been widely investigated for optical memory storage and switches. Very recently, we pioneeringly discovered optical control of ferroelectric polarization switching in organic photochromic salicylaldehyde Schiff base and diarylethene derivatives, differently from the traditional ferroelectrics. However, the study of such intriguing photo-triggered ferroelectrics is still in its infancy and relatively scarce. In this manuscript, we synthesized a pair of new organic single-component fulgide isomers, ( E and Z )-3-(1-(4-( tert -butyl)phenyl)ethylidene)-4-(propan-2-ylidene)dihydrofuran-2,5-dione (1E and 1Z). They undergo prominent photochromism from yellow to red. Interestingly, only polar 1E has been proven to be ferroelectric, while the centrosymmetric 1Z does not meet the basic requirement for ferroelectricity. Besides, experimental evidence shows that the Z -form can be converted to the E -form by light irradiation. More importantly, the ferroelectric domains of 1E can be manipulated by light in the absence of an electric field, benefiting from the remarkable photoisomerization. 1E also adopts good fatigue resistance to the photocyclization reaction. As far as we know, this is the first example of organic fulgide ferroelectric reported with photo-triggered ferroelectric polarization response. This work has developed a new system for studying photo-triggered ferroelectrics and would also provide an expected perspective on developing ferroelectrics for optical applications in trap future., Competing Interests: The authors declare no competing financial interest., (© 2023 The Authors. Published by American Chemical Society.)

Regioselective silylation of 2,3-allenols with disilanes was carried out under catalysis of Pd 2 dba 3 /P( o -MeOC 6 H 4 ) 3 . In the presence of Cs 2 CO 3 , the reaction achieved 2-silyl-1,3-dienes. Reaction of 1-aryl-2,3-allenols gave the products with excellent Z / E selectivity and E -isomers as the major species. Reaction of α-alkylallenols or α-alkyl-α-aryl-allenols resulted in products with moderate Z / E selectivity and E -isomers are also major. Without a base, the reaction produced α-silyl-β-hydroxyl vinylsilanes, which were converted to 2-silyl-1,3-dienes upon treatment with Cs 2 CO 3 .

Organic-inorganic hybrid metal halide perovskites possessing unique two-dimensional (2D)-layered structures have been demonstrated with excellent molecular tunability and stability, especially the promising semiconductor properties for solar cell applications. In this work, three 2D lead halide organic-inorganic hybrid perovskites (IAA) 2 PbX 4 (IAA = isoamylammonium cation and X = Cl, Br, and I) were synthesized by employing a solution processing method and demonstrate distinct tuning solid-state phase transitions coupled with dielectric responses, as well as light absorption properties. Among the title perovskites, the phase transition temperature decreases gradually, and their band gap also indicates a narrowing trend. The results are mainly derived from slight changes in the crystal structure by halogen regulation. These findings might provide an effective crystal engineering strategy for exploring high-performance functional perovskite materials.

Organic-inorganic hybrid lead halide perovskites have attracted great interest for their use in promising optoelectronic applications. However, reports of photoluminescent perovskite molecular ferroelastic semiconductors with sequential high- T c phase transitions have been scarce. In this work, a one-dimensional lead bromide hybrid perovskite [ N,N -dimethylethanolammonium]PbBr 3 has been synthesized, undergoing high- T c sequential phase transitions at around 351 and 444 K, higher than those of most previously discovered hybrid perovskite phase transition materials. The specific intermolecular hydrogen bond between cationic molecules provides the greatest contribution to its high T c by increasing the barrier of molecular motion under the temperature stimuli. The prominent ferroelastic domain evolution is visually observed under orthogonally polarized light. In addition, [ N,N -dimethylethanolammonium]PbBr 3 exhibits semiconducting and orange light emission characteristics. This finding opens up an avenue for designing high-performance ferroelastic materials and provides great motivation for discovering new multifunctional materials for the next generation of smart devices.

Piezoelectric materials with inherent mechanical-electric coupling effect are a crucial family of functional materials in high-end information technology. For practical applications, the transverse piezoelectric performance ( d 31 or d 32 ) is mainly considered, because this parameter is a vitally important index to characterize the performance of piezoelectric thin films. However, the transverse piezoelectricity of the thin films as a key figure of merit is seldom mentioned in molecular ferroelectrics. Herein, we report that a new 1D halide perovskite ferroelectric N , N -dimethylallylammoniumCdCl 3 (DMAACdCl 3 ) exhibits an above room-temperature ferroelectric phase transition with a saturated polarization of 1.9 μC cm -2 and a coercive field of 5.0 kV cm -1 . The thin film of DMAACdCl 3 is successfully fabricated using an easy processing spinning method and maintains well ferroelectric properties verified by piezoresponse force microscopy (PFM). More significantly, the ferroelectric thin film offers superior transverse piezoelectricity with an in-plane piezoelectric response of about 41 pC N -1 , which is about twice that of well-known piezoelectric polymer PVDF (21 pC N -1 ). Transverse piezoelectricity has been scarcely studied in molecular ferroelectrics, and its exploitation would play an important role in the design of next-generation smart piezoelectric devices.

By choosing different phosphine ligands, nickel-catalyzed selective alkylation and reduction of allylic alcohols with alkyl Grignard reagents were performed. The reaction using Ni(dppe)Cl 2 as the catalyst resulted in the cross-coupling of allylic alcohols with primary alkyl Grignard reagents and cyclopropylmagnesium bromide. The reaction catalyzed by the combination of Ni(PCy 3 ) 2 Cl 2 and dcype led to the reduction of allylic alcohols. Secondary alkyl Grignard reagents except cyclopropylmagnesium bromide always led to reduction of allylic alcohols using either Ni(dppe)Cl 2 or Ni(PCy 3 ) 2 Cl 2 /dcype as the catalyst. In the reductive reaction β-H-containing alkyl Grignard reagents were required.

NiCl 2 (PMe 3 ) 2 -catalyzed reaction of allyl alcohols with silylzinc reagents, including PhMe 2 SiZnCl, Ph 2 MeSiZnCl, and Ph 3 SiZnCl, was performed, achieving allylsilanes in high yields. Aryl- and heteroaryl-substituted allyl alcohols, ( E )-3-arylprop-2-en-1-ols, 1-aryl-prop-2-en-1-ols, and ( E )-1-phenylpent-1-en-3-ol can be employed in the transformation. A range of functional groups as well as heteroaryl groups were tolerated. Reaction exhibited high regioselectivity and E / Z -selectivity when 1- or 3-aryl-substituted allyl alcohols were used as the substrates. Reaction of chiral allyl alcohol, ( S , E )-1-phenylpent-1-en-3-ol, yielded a configuration-inversion product ( R , E )-dimethyl(phenyl)(1-phenylpent-1-en-3-yl)silane.

Antiperovskites have developed to be one kind of important functional material over the past few decades, showing abundant physical properties such as negative thermal expansion and superconductivity, etc. However, antiperovskite ferroelectrics have scarcely been discovered in inorganic ceramics. In this article, we report a new organic-inorganic hybrid antiperovskite ferroelectric [(CH 3 ) 2 (F-CH 2 CH 2 )NH] 3 (CdCl 3 )(CdCl 4 ) based on the strategy of molecular design. The replacement of one methyl in [(CH 3 ) 3 NH]CdCl 3 with ethyl produces the lower symmetric [(CH 3 ) 2 (CH 2 CH 3 )NH]CdCl 3 with nonpolar perovskite structure, while the polar hexagonal antiperovskite structure with the formula of X 3 BA (where X = [(CH 3 ) 2 (F-CH 2 CH 2 )NH] + , B = [CdCl 3 ] - , and A = [CdCl 4 ] 2- ) was received after further fluoridation of the ethyl group. Therefore, fluoridation successfully achieves the structural transformation from perovskite to antiperovskite, as well as the significant changes in physical properties from nonferroelectric to ferroelectric. The antiperovskite [(CH 3 ) 2 (F-CH 2 CH 2 )NH] 3 (CdCl 3 )(CdCl 4 ) exhibits typical ferroelectric phase transition above room temperature ( T c = 333 K) including thermal anomalies, dielectric transitions, and second harmonic generation (SHG) responses. Moreover, lower coercive fields and easy polarization switching are observed by the measurements of hysteresis loops and ferroelectric domains. The saturated polarization ( P s ) of 4.0 μC/cm 2 is almost 10 times as large as those recently discovered antiperovskite molecular ferroelectrics. This finding provides a novel strategy to design and explore more antiperovskite organic-inorganic hybrid ferroelectric materials.

Cross-coupling of (hetero)arylthiols with arylzinc reagents via C-S cleavage was performed under transition-metal-free conditions. The reaction displays a wide scope of substrates and high functional-group tolerance. Electron-rich and -deficient (hetero)arylthiols and arylzinc reagents can be employed in this transformation. Mg 2+ and Li + ions were demonstrated to facilitate the reaction.

Reaction of aryl 2-pyridyl ethers with amines was carried out via Ni-catalyzed C-O Py bond cleavage, giving aniline derivatives in reasonable to excellent yields. Both electron-rich and electron-poor aryl 2-pyridyl ethers and a wide range of amines can be used in the transformation. The method provides a conversion way for the 2-pyridyloxy directing group in the C-H bond functionalization reactions.

Molecular optical-electrical duple switches (switch "ON" and "OFF" bistable states) represent a class of highly desirable intelligent materials because of their sensitive switchable physical and/or chemical responses, simple and environmentally friendly processing, light weights, and mechanical flexibility. In the current work, the phase transition of 1 (general formula R2MX5, [C5N2H16]2[SbBr5]) can be triggered by the order-disorder transition of the organic cations at 278.3 K. The temperature-induced phase transition causes novel bistable optical-electrical duple characteristics, which indicates that 1 might be an excellent candidate for a potential switchable optical-electrical (fluorescence/dielectric) material. In the dielectric measurements, remarkable bistable dielectric responses were detected, accompanied by striking anisotropy along various crystallographic axes. For the intriguing fluorescence emission spectra, the intensity and position changed significantly with the occurrence of the structural phase transition. We believe that these findings might further promote the application of halogenoantimonates(III) and halogenobismuthates(III) in the field of optoelectronic multifunctional devices.

The P,N,N-pincer nickel complex [Ni(Cl){N(2-Ph2PC6H4)(2'-Me2NC6H4)}]-catalyzed allyl-aryl coupling was studied. The reaction of allyl methyl ethers, including (1-methoxyallyl)arenes and (3-methoxyprop-1-en-1-yl)arenes, with arylzinc chlorides afforded linear (E)-alkenes in high yields, whereas the reaction of (E)-1-methoxytridec-2-ene with p-Me2NC6H4ZnCl generated a mixture of linear and branched alkenes.

The C-H arylation of (benzo)oxazoles or (benzo)thiazoles with aryltrimethylammonium triflates was carried out via Pd-catalyzed C-H/C-N cleavage. Oxazoles, thiazoles, benzoxazole, and benzothiazole were arylated using activated and deactivated aryltrimethylammonium triflates to give 2-aryl(benzo)oxazoles or 2-aryl(benzo)thiazoles in reasonable to excellent yields.

Palladium-catalyzed cross-coupling via the C(sp(2))-S bond activation of aryl thioethers and the C-H bond activation of azoles or thiazoles was carried out. Electron-deficient and -rich aryl methyl thioethers and diaryl thioethers can be employed as the coupling partners and the reaction tolerates a range of functional groups including MeO, CF3, CN, PhCO, CONEt2, and Py groups.

This work reports on a facile, economical, and green preparative strategy toward water-soluble, fluorescent oxygen-doped, nitrogen-rich, photoluminescent polymer carbon nanoribbons (ONPCRs) with a quantum yield of approximately 25.61% by the hydrothermal process using uric acid as a carbon-nitrogen source for the first time. The as-prepared fluorescent ONPCRs showed paddy leaf-like structure with 80-160 nm length and highly efficient fluorescent quenching ability in the presence of mercury(II) (Hg(2+)) or silver (Ag(+)) ions due to the formed nonfluorescent metal complexes via robust Hg(2+)-O or Ag(+)-N interaction with the O and N of fluorescent ONPCRs, which allowed the analysis of Hg(2+) and Ag(+) ions in a very simple method. By employing this sensor, excellent linear relationships existed between the quenching degree of the ONPCRs and the concentrations of Hg(2+) and Ag(+) ions in the range of 2.0 nM to 60 μM and 5.0 nM to 80 μM, respectively. By using ethylenediaminetetraacetate and ammonia as the masking agent of Hg(2+) and Ag(+) ions, respectively, Hg(2+) or Ag(+) ions were exclusively detected in coexistence with Ag(+) or Hg(2+) ions with high sensitivity, and the detection limits as low as 0.68 and 1.73 nM (3σ) were achieved, respectively, which also provided a reusable detection method for Hg(2+) and Ag(+) ions. Therefore, the easily synthesized fluorescent ONPCRs may have great potential applications in the detection of Hg(2+) and Ag(+) ions for biological assay and environmental protection.

Ni(PCy3)2Cl2 was demonstrated to effectively catalyze cross-coupling of aryl fluorides and organozinc reagents. Both electron-poor and -rich aryl fluorides can react effectively with nucleophiles including aryl-, methyl-, and benzylzinc chlorides. A wide range of substituents and functional groups are tolerated. In the presence of a directing group, PhC(O), the reaction is selective for cleavage of the C-F bond ortho to the carbonyl substituent in a difluoroarene.

Utilizing the principles of metal-ion-mediated base pairs (C-Ag-C and T-Hg-T), the pH-sensitive conformational transition of C-rich DNA strand, and the ligand-exchange process triggered by DL-dithiothreitol (DTT), a system of colorimetric logic gates (YES, AND, INHIBIT, and XOR) can be rationally constructed based on the aggregation of the DNA-modified Au NPs. The proposed logic operation system is simple, which consists of only T-/C-rich DNA-modified Au NPs, and it is unnecessary to exquisitely design and alter the DNA sequence for different multiple molecular logic operations. The nonnatural base pairing combined with unique optical properties of Au NPs promises great potential in multiplexed ion sensing, molecular-scale computers, and other computational logic devices.

N-Heterocyclic carbene-based pincer nickel complexes were synthesized and characterized. These complexes efficiently catalyze cross-coupling of aryl Grignard reagents with aryl chlorides or fluorides under mild conditions.

The cross-coupling reaction of aryltrimethylammonium iodides with aryl- or heteroarylzinc chlorides catalyzed by amido pincer nickel complexes was performed. The reaction requires low catalyst loading and displays broad substrate scope.

A series of amido pincer complexes of nickel were examined for their catalysis in the Kumada cross-coupling reaction. The P,N,O-pincer nickel complexes tested are active catalysts for the cross-coupling of aryl, heteroaryl, and vinyl chlorides with aryl Grignard reagents. The reactions can proceed at room temperature and tolerate functional groups in aryl chlorides with the aid of LiCl and ZnCl(2) additives.

The nickel-catalyzed Negishi cross-coupling reaction of aryl chlorides with arylzinc compounds was investigated. The nickel complexes with the amido pincer type of ligands exhibited high catalytic activity and good functional group tolerance.

Reaction of MCl4 (M = Zr, Hf) with 2 equiv of 2-iminophosphorano-1-phosphaallyl lithium [Li[P(Ph)C(=CHPh)P(Me)2=NSiMe3](THF)1.5] (1) affords ligand coupling complexes 3 and 4, respectively, while similar treatment of ZrCl4 with [Li[P(Ph)C(=C(SiMe2Bu(t))Ph)P(Me)2=NSiMe3](THF)2] (2) yields ligand transfer complex 5.