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1.
Artigo em Inglês | MEDLINE | ID: mdl-35025213

RESUMO

Exploring new infrared nonlinear optical (IR NLO) materials with superior overall properties is scientifically and technically important. However, large second-order harmonic generation (SHG) efficiencies and high laser-induced damage thresholds (LIDT) are incompatible, which makes realizing this goal a challenge. The IR NLO performance of an A-NIIB-MIIIA-Q (Q: chalcogen) system was optimized by simultaneously modulating A/(M + N) and M/N ratios (A: alkali metal; N, M: tetra-coordinated metals), and SHG-LIDT balance was achieved. Three new sulfides, KCd3Ga5S11 (1), RbCd4Ga3S9 (2), and Cs2Cd2Ga8S15 (3), containing the same CdS4 and GaS4 but with different A/(Ga + Cd) and Ga/Cd ratios were obtained. Among these compounds, compound 3 exhibits both the largest SHG efficiency (0.5 × AgGaS2) and LIDT (35 × AgGaS2), which can be ascribed to the Ga/Cd modulation for enhancing the NLO functional motif distortions and SHG efficiency as well as the A/(Ga + Cd) modulation for enlarging the band gap and LIDT. Remarkably, compound 3 is the first phase-matchable IR NLO material in the A-NIIB-MIIIA-Q family. This article proposes a novel avenue to explore infrared nonlinear materials with superior comprehensive properties by modulating the A/(M + N) and M/N ratios.

2.
Inorg Chem ; 2021 Dec 28.
Artigo em Inglês | MEDLINE | ID: mdl-34962374

RESUMO

Detection of oxygen though color change is highly desirable for rapid qualitative analysis like the case of pH test papers. This work demonstrates 3O2-assisted photoinduced color change of a new photochromic coordination compound [Zn(4-aminopyridine)2Cl2] (ZnaPyCl), which represents the first photochromic compound with a selective 3O2 detection ability. The compound underwent photoinduced intraligand charge separation and formed a stable diradical-like triplet species in the solid state or in frozen solution, accompanied by conversion of triplet oxygen to singlet oxygen.

3.
Nanoscale ; 13(44): 18773-18779, 2021 Nov 18.
Artigo em Inglês | MEDLINE | ID: mdl-34747962

RESUMO

Production of ethylene glycol from coal is a particularly interesting route as it is an economic alternative to the petrochemical-based route. In this process, effectively generating dimethyl oxalate (DMO) is a crucial step by CO oxidative coupling reaction under Pd-based catalysts. However, the aggregation of Pd species over the support is still an issue that relates to the deterioration of catalytic activity and stability. To this end, enhancing the metal-support interaction is urgently required. In this work, hierarchical Nb2O5 (H-Nb2O5) microspheres with abundant oxygen defects were synthesized to anchor the Pd species thus promoting the electron transfer between Pd species and Nb species associated with the generation of interfacial Pd-NbOx sites. Besides, the thinned electron density of Pd species resulting from the electron-withdrawing effect of Nb species is beneficial for activating the adsorbed CO molecules, leading to superior catalytic activity. The Pd/H-Nb2O5 catalyst exhibited 63.1% of CO conversion (theoretical maximum conversion: 64.3%) and 92.9% of DMO selectivity, with a DMO weight time yield of 1297.9 g kgcat.-1 h-1, and remained robust even after 50 h of time on stream evaluation. Current work provides a deep insight into the CO activation mechanism and helps improve the catalytic stability by boosting interfacial electron interaction via oxygen defects induction, and also sheds light on the design and synthesis of high-performance catalysts in other heterogeneous catalysis fields.

4.
Mater Horiz ; 8(12): 3394-3398, 2021 Nov 29.
Artigo em Inglês | MEDLINE | ID: mdl-34676385

RESUMO

The nonlinear optical (NLO) efficiency (dij) and laser-induced damage threshold (LIDT) of a material are mainly determined by their covalency and ionicity, respectively, the incompatibility between which makes balancing the dij and LIDT challenging in an IR NLO material. The topological feature (fractal dimension) of the electron localization function (ELF) map (distribution of covalency and ionicity) was evaluated for a series of NLO materials, and, phenomenologically, the fine mixing of covalency and ionicity will benefit a balanced dij and LIDT. Chemical bonds with different interaction strengths were introduced simultaneously to mix the covalency and iconicity finely, and three new IR NLO sulfides, A2Ba3Li6Ga28S49 (A = K, 1; Rb, 2; Cs, 3), were obtained. They exhibit a strong NLO efficiency (1.9-2.1 × AgGaS2 at 1064 nm and 0.5-0.6 × AgGaS2 at 1910 nm) and high LIDTs (16.7-18.0 × AgGaS2), which fulfill the criteria of being promising IR NLO candidates. This study provides a new method for designing high-performance IR NLO materials based on the topological features of the ELF.

5.
Inorg Chem ; 60(13): 9278-9281, 2021 Jul 05.
Artigo em Inglês | MEDLINE | ID: mdl-34142822

RESUMO

A high contrast of ∼67 times, exceeding those of all known photoswitching bulk quadratic nonlinear-optical materials, has been realized in a photochromic semiconductor, by the strategy of increasing electron-transfer efficiency and self-absorption.

6.
Angew Chem Int Ed Engl ; 60(33): 18223-18230, 2021 Aug 09.
Artigo em Inglês | MEDLINE | ID: mdl-34114311

RESUMO

Similarities in sizes, shapes, and physical properties between carbon dioxide (CO2 ) and acetylene (C2 H2 ) make it a great challenge to separate the major impurity CO2 from products in C2 H2 production. The use of porous materials is an appealing path to replace current very costly and energy-consuming technologies, such as solvent extraction and cryogenic distillation; however, high CO2 /C2 H2 uptake ratio with minor adsorption of C2 H2 at standard pressure was only unexpectedly observed in scarce examples in recent years although the related research started early at 1950s, and general design strategies to realize this aim are still absent. This work has successfully developed an efficient PIET strategy and obtained the second highest CO2 /C2 H2 adsorption ratio for porous materials in a proof-of-concept MOF with a photochromism-active bipyridinium zwitterion. An unprecedented photocontrollable gate effect, owing to change of interannular dihedral after photoinduced generation of radical species, was also observed for the first time. These findings will inspire design and synthesis of porous materials for high efficient gas adsorption and separation.

7.
Chem Commun (Camb) ; 57(45): 5550-5553, 2021 Jun 03.
Artigo em Inglês | MEDLINE | ID: mdl-33969841

RESUMO

A new design strategy through the synergy of Mo(vi)-Mo(v) intervalence charge transfer and π(radical)-π(radical/cation) interactions is proposed to obtain semiconductors with photoresponsive ranges covering the whole UV-SWIR (ultraviolet-shortwave near-infrared; ca. 250-3000 nm) region. With this strategy, a viologen-based molybdate semiconductor with a UV-SWIR photoresponsive range was obtained through UV/X-ray irradiation or thermal annealing. The thermally annealed semiconductor has the highest conversion and the best photocurrent response in the range of 355-2400 nm.

8.
ACS Appl Mater Interfaces ; 13(21): 24856-24864, 2021 Jun 02.
Artigo em Inglês | MEDLINE | ID: mdl-34009944

RESUMO

Strong metal-support interaction is crucial to the stability of catalysts in heterogeneous catalysis. However, reports on boosting interfacial electron transfer between metal and support via defect induction for enhanced metal-support interaction are limited. In this work, ultrathin reducible ZnTi-layered double hydroxide (LDH) nanosheets with rich oxygen defects were synthesized to stabilize Pd clusters, and the rich oxygen defects promoted Pd cluster bonding with Zn and Ti atoms in supports, thereby forming a metal-metal bond. Electron spin resonance (ESR), X-ray absorption fine spectra (XAFS), and density functional theory (DFT) calculations demonstrate remarkable interfacial electron transfer (0.62 e). The Pd/ZnTi-LDH catalyst shows superior catalytic stability for CO direct esterification to dimethyl oxalate. By contrast, the nonreducible Pd/ZnAl-LDH catalyst with a few oxygen defects shows minimal interfacial electron transfer (0.08 e), which leads to relatively poor catalytic stability. This work provides a deep insight into promoting the stability of catalysts by boosting interfacial electron transfer via defect induction.

9.
Inorg Chem ; 60(8): 5538-5544, 2021 Apr 19.
Artigo em Inglês | MEDLINE | ID: mdl-33830749

RESUMO

Photoresponse ranges of commercially prevailing photoelectric semiconductors, typically Si and InGaAs, are far from fully covering the whole solar spectrum (∼295-2500 nm), resulting in insufficient solar energy conversion or narrow wave bands for photoelectric detection. Recent studies have shown that infinite π-aggregation of viologen radicals can provide semiconductors with a photoelectric response range covering the solar spectrum. However, controlled assembly of an infinite π-aggregate is still a great challenge in material design. Through directional self-assembly of electron-transfer photoactive polycyclic ligands, two crystalline inorganic-organic hybrid photochromic viologen-based bismuth halide semiconductors, ((Me)3pytpy)[BiCl6]·2H2O [1; (Me)3pytpy = N,N',N″-trimethyl-2,4,6-tris(4-pyridyl)pyridine] and ((Me)3pytpy)[Bi2Cl9]·H2O (2), have been synthesized. They represent the first series of pytpy-based photochromic compounds. After photoinduced coloration, the conductivities of both 1 and 2 increased. The radical products have electron absorption bands in the range of 200-1600 nm, exceeding that of Si. Both the conductivity and the photocurrent intensity of 2 are stronger than those of 1, due to better planarity, tighter π-stacking, and higher degrees of overlap of ((Me)3pytpy)3+ cations. This study not only provides a new design idea for synthesizing radical-based multispectral photoelectric semiconductors but also enriches the family of electron-transfer photochromic compounds.

10.
Angew Chem Int Ed Engl ; 60(21): 11799-11803, 2021 May 17.
Artigo em Inglês | MEDLINE | ID: mdl-33749981

RESUMO

Exploring nonlinear optical (NLO) functional motifs (FM, the structural origin of NLO efficiency) is vital for the rational design of NLO materials. Normal spectrum techniques applied in studying photon exciting materials are invalid for NLO materials, in which electrons are not excited substantially but only distorted under laser. A general strategy of determining NLO FM is proposed by comparative studies of experimental electron density (ED) without and under the laser. The in situ experimental ED and wavefunction of typical NLO material LiB3 O5 (LBO) under dark and 360 and 1064 nm lasers are investigated. Compared with the initial state under dark, the ED of [B3 O5 ]- unit at functional states under laser irradiation exhibits remarkable changes of topological atomic and bond properties, confirming the NLO FM being [B3 O5 ]- . The work extracts for the first time the FM of a NLO material experimentally and highlights the crucial role of in situ ED analysis in studying NLO mechanisms.

11.
J Am Chem Soc ; 143(5): 2232-2238, 2021 02 10.
Artigo em Inglês | MEDLINE | ID: mdl-33522242

RESUMO

Charge-separated states with a lifetime scale of seconds or longer not only favor studies using various steady-state analysis techniques but are important for light-energy conversion and other applications. Through a steric-hindrance-induced method, unprecedented photoinduced generation of a partially charge separated (PCS) state with a lifetime of days has been detected in the "visual" mode during the decay of excited states to a commonly observed fully charge separated (FCS) state for viologen analogues. One pale yellow 4,4'-bipyridine-based metalloviologen compound, with an interannular dihedral angle of 1.84° in 4,4'-bipyridine, directly decays to the purple FCS state after photoexcitation. The other pale yellow compound, with a similar coordination framework but a larger interannular dihedral angle (33.74°), changes first to a yellow PCS state and then relaxes slowly (in the dark in Ar, ca. 2 days; 70 °C in Ar, ca. 1 h) to the purple FCS state. The two-step coloration phenomenon is unprecedented for viologen compounds and their analogues and also rather rare for other photochromic species. EPR and Raman data reveal that photoinduced charge separation first generates univalent zinc and radicals and then the received electron in Zn(I) slowly distributes further to 4,4'-bipyridine. Reduction of π-conjugation and a direct to indirect change in band gap account for the prolongation of the relaxation process and the capture of the PCS state. These findings help to understand and control decay processes of excited states and provide a potential design strategy for multicolor photochromism, light-energy conversion with high efficiency, or other applications.

12.
Inorg Chem ; 60(2): 560-564, 2021 Jan 18.
Artigo em Inglês | MEDLINE | ID: mdl-33411521

RESUMO

Photochromic open-framework compounds are of potential application in detection/sensors. The issue of improving the detection limits has received much attention. We synthesized a new open-framework Zn compound, namely, compound 1 ([Zn(MQ)(IPA)Cl]·5H2O) (MQ = N-methyl-4,4'-bipyridinium, IPA = m-phthalic acid), which showed a 1D channel structure by a cationic-π interaction. It is noteworthy that this compound is an effective detector for aniline though luminescence emission, which exhibited unprecedented detection limits in photochromic open-framework compounds.

13.
Artigo em Inglês | MEDLINE | ID: mdl-33169978

RESUMO

Exploration of a new nonlinear optical (NLO)-active functional motif is important in the rational design of promising infrared (IR) NLO materials. Compared with typical tetrahedral MQ4 (M = IIB, III, IV metals; Q = S, Se) motifs, MQ3 (M = As, Sb) pyramids favor high second-harmonic generation (SHG) efficiency while frequently hindering phase matching (PM) because of excessively large optical anisotropy. The surfactant-thermal method was first adopted to achieve PM in MQ3-containing systems and synthesize mixed covalent-ionic IR NLO materials. Two new thioarsenates of AMnAs3S6 (A = Cs, Rb) exhibiting strong PM SHG efficiencies comparable to commercial AGS and laser-induced damage thresholds of one order higher than AGS were obtained. The [As3S6]3- unit in their structures is an unprecedented NLO-active functional motif, which can be useful in designing new IR NLO compounds with large SHG efficiency. In addition, the surfactant-thermal method provides a new general strategy for synthesizing new IR NLO materials.

14.
Chem Commun (Camb) ; 56(93): 14689-14692, 2020 Nov 24.
Artigo em Inglês | MEDLINE | ID: mdl-33165482

RESUMO

Utilization of photochromism in photo-switchable white-light emitters (WLEs) is a challenging task. In an effort to achieve this, we have recently developed a new Gd-MOF using a photoactive pyridinium-based inner salt. The compound shows interesting photoswitchable bluish white light to greenish yellow light emission as a result of electron transfer, a phenomenon that has not been observed previously in photochromic crystal compounds.

15.
Nanoscale ; 12(39): 20131-20140, 2020 Oct 15.
Artigo em Inglês | MEDLINE | ID: mdl-32749438

RESUMO

The direct esterification of CO involves processes using CO as the starting material and ester chemicals as products. Dimethyl oxalate (DMO) and dimethyl carbonate (DMC) are two different products of the direct CO esterification reaction. However, the effective control of the reaction pathway and direct synthesis of DMO and DMC are challenging. In this review, we summarize the recent research progress on the direct esterification of CO to DMO/DMC and reveal the functional motifs responsible for the catalytic selectivity. Firstly, we discuss the microstructure of catalysts for the direct esterification of CO to DMO and DMC, including the valence state and the aggregate state of Pd. Then, the influence of characteristics of the support on the selectivity is analyzed. Importantly, the aggregate state of the active component, Pd is deemed as a vital functional motif for catalytic selectivity. The isolated Pd is conducive for the formation of DMC, while the aggregated Pd is beneficial for the formation of DMO. This review will provide rational guidance for the direct esterification of CO to DMO and DMC.

16.
Nanoscale ; 12(27): 14825-14830, 2020 Jul 16.
Artigo em Inglês | MEDLINE | ID: mdl-32672320

RESUMO

Pd-Based heterogeneous catalysts have been demonstrated to be efficient in numerous heterogeneous reactions. However, the effect of the support resulting in covalent metal-support interaction (CMSI) has not been researched sufficiently. In this work, a Lewis base is modulated over MgAl-LDH to investigate the support effects and it is further loaded with Pd clusters to research the metal-support interactions. MgAl-LDH with ultra-low Pd loading (0.0779%) shows CO conversion (55.0%) and dimethyl oxalate (DMO) selectivity (93.7%) for CO oxidative coupling to DMO, which was gradually deactivated after evaluation for 20 h. To promote the stability of Pd/MgAl-LDH, Zn2+ ions were introduced into the MgAl-LDH support to strengthen the CMSI by forming Pd-Zn bonds, which further increased the adsorption energy of the Pd clusters on ZnMgAl-LDH, and this was verified by X-ray absorption fine structure (XAFS) measurements and density functional theory (DFT) calculations. The stability of the Pd/ZnMgAl-LDH catalyst could be maintained for at least 100 h. This work highlights that covalent metal-support interactions can be strengthened by forming new metal-metal bonds, which could be extended to other systems for the stabilization of noble metals over supports.

17.
Dalton Trans ; 49(22): 7309-7314, 2020 Jun 09.
Artigo em Inglês | MEDLINE | ID: mdl-32458956

RESUMO

The synergy of unusual X-aggregation induced luminescent chromophores and heavy Pb(ii) ions has facilitated excellent X-ray scintillation of two structurally similar Pb-SMOFs, which are heat-resistant due to solvent-free lattices. Owing to their higher Pb(ii) contents, Pb-SMOFs with larger X-ray absorption coefficients are more sensitive for X-ray dosage detection than powdered CsPbBr3.

18.
J Am Chem Soc ; 142(24): 10641-10645, 2020 Jun 17.
Artigo em Inglês | MEDLINE | ID: mdl-32469217

RESUMO

Noncentrosymmetry (NCS) is a prerequisite for second-order nonlinear optical (NLO) materials. In this work, a new polycation-substitution-induced centrosymmetry (CS)-to-NCS transformation strategy was applied in CS RbGaS2, affording two novel NCS salt-inclusion chalcogenides: [ABa2Cl][Ga4S8] (A = Rb, 1; Cs, 2). Remarkably, they exhibit the key merits of both Vis and IR NLO candidates, including strong phase-matchable second harmonic generation intensities (10.4-15.3 × KH2PO4 at 1064 nm; 0.9-1.0 × AgGaS2 at 1910 nm), high laser-induced damage thresholds (11-12 × AgGaS2), and a wide transparent window. Their prominent NLO performances originate from the orderly packing of T2-supertetrahedral Ga4S10 motifs resulting from the template effect of acentric polycation [ClA2Ba3]7+. The CS-to-NCS transformation first realized by polycation-substitution-induced NLO-functional motif ordering provides an effective approach for designing new NLO materials.

19.
Nat Commun ; 11(1): 1179, 2020 Mar 04.
Artigo em Inglês | MEDLINE | ID: mdl-32132532

RESUMO

Extending photoresponse ranges of semiconductors to the entire ultraviolet-visible (UV)-shortwave near-infrared (SWIR) region (ca. 200-3000 nm) is highly desirable to reduce complexity and cost of photodetectors or to promote power conversion efficiency of solar cells. The observed up limit of photoresponse for organic-based semiconductors is about 1800 nm, far from covering the UV-SWIR region. Here we develop a cyanide-bridged layer-directed intercalation approach and obtain a series of two viologen-based 2D semiconductors with multispectral photoresponse. In these compounds, infinitely π-stacked redox-active N-methyl bipyridinium cations with near-planar structures are sandwiched by cyanide-bridged MnII-FeIII or ZnII-FeIII layers. Radical-π interactions among the infinitely π-stacked N-methyl bipyridinium components favor the extension of absorption range. Both semiconductors show light/thermo-induced color change with the formation of stable radicals. They have intrinsic photocurrent response in the range of at least 355-2400 nm, which exceeds all reported values for known single-component organic-based semiconductors.

20.
Nanoscale ; 12(8): 4771-4789, 2020 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-32064483

RESUMO

One-dimensional (1D) inorganic-organic metal halide hybrids at the molecular level, which can be considered as arrays of nanochains isolated by organic components, have shown remarkable optical and electric properties. This review summarizes their reported structural types and shows how to modify their band gaps and optical and electric properties.

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