Construction of multivariate donor-acceptor heterojunction in covalent organic frameworks for enhanced photocatalytic oxidation:Regulating electron transfer and superoxide radical generation

Covalent organic frameworks(COFs)have attracted attention as photocatalysts,however,low electron transfer and reactive oxygen species(ROS)generation still hinder their photocatalytic application.In this work,we construct multivariate donor-acceptor(D-A)heterojunctions in the covalent organic frameworks by synchronously introducing electron-withdrawing and donating substituents.Importantly,the optoelectronic characteristics and visible-light photocatalytic performance were improved with the increase of the electron donor carbon chains in multivariate D-A COFs.Combining in‐situ characterization with theoretical calculations,the charge carrier separation and transfer efficiency,•O_(2)–generation and conversion,and the energy barrier of the rate determination steps related to the formation of*OH and*OOH,can be well regulated by the multivariate D-A COFs.More importantly,the ortho-carbon atom of the Br and OCH_(3) group-linked benzene rings and the imine bond(–C=N–)in COF-Br@OCH_(3) were activated to produce the key*OH and*OOH intermediates for effectively reducing the energy barrier of H2O oxidation and O_(2) reduction.This work provides valuable insights into the precise design and synthesis of COFs-based catalysts and the regulation of electron transfer and ROS generation by modulating the electron-withdrawing and donating substituents for highly efficient visible-light photocatalytic degradation of refractory organic pollutants.

Decarboxylative cyanation and thiocyanation via catalytic electron donor-acceptor complex with copper catalysis

A new catalytic decarboxylative cyanation and thiocyanation via a synergistic Na I/Cu catalysis is developed.The photoexcited electron donor-acceptor complex by assembly of Na I,R3P,and N-acyloxy-phthalimide ester(NHPI ester)triggers the generation of alkyl radical species,which then engages in Cu-catalyzed radical coupling process.Key to success of this dual catalytic transformation is the reliable charge transfer between I·and Cu(I).This dual catalytic platform can eliminate the use of expensive iridium-based photocatalyst or synthetically elaborate organic dyes.A series of primary,secondary,and tertiary alkyl nitriles and thiocyanates are easily synthesized.Moreover,an asymmetric decarboxylative cyanation by applying a chiral Cu catalyst is also developed to afford chiral nitriles in high enantioselectivity.The mechanistic details and the origin of the high enantioselectivity are further investigated by the mechanistic experiments and the density functional theory calculations.

推、拉电子基团对水杨醛缩苯胺分子电子结构和非线性光学性质的影响

采用量子化学半经验FF/PM3方法 ,讨论了水杨醛缩苯胺分子中两苯环的对位被推、拉电子基团取代后 ,体系电子结构和非线性光学性质的变化 .考查了分子电子结构对非线性光学性质影响的微观本质 ,得到的具有给体 -共轭桥键

推、拉电子基团对水杨醛缩苯胺及其衍生物分子的电子结构和非线性光学性质的影响

采用量子化学半经验FF/PM3方法,讨论了水杨醛缩苯胺分子中两个苯环的对位被推、拉电子基团取代后,体系电子结构和非线性光学性质的变化.考察了分子的电子结构对非线性光学性质影响的微观本质,结果表明:得到的具有配体-共轭桥键-受体型结构的水杨醛缩苯胺分子显示了良好的非线性光学性质.

Chemical Reactivity Description in Density-Functional and Information Theories

In Quantum Information Theory(QIT) the classical measures of information content in probability distributions are replaced by the corresponding resultant entropic descriptors containing the nonclassical terms generated by the state phase or its gradient(electronic current). The classical Shannon(S[p]) and Fisher(I[p]) information terms probe the entropic content of incoherent local events of the particle localization, embodied in the probability distribution p, while their nonclassical phase-companions, S[ Φ ] and I[ Φ ], provide relevant coherence information supplements.Thermodynamic-like couplings between the entropic and energetic descriptors of molecular states are shown to be precluded by the principles of quantum mechanics. The maximum of resultant entropy determines the phase-equilibrium state, defined by "thermodynamic" phase related to electronic density,which can be used to describe reactants in hypothetical stages of a bimolecular chemical reaction.Information channels of molecular systems and their entropic bond indices are summarized, the complete-bridge propagations are examined, and sequential cascades involving the complete sets of the atomic-orbital intermediates are interpreted as Markov chains. The QIT description is applied to reactive systems R = A―B, composed of the Acidic(A) and Basic(B) reactants. The electronegativity equalization processes are investigated and implications of the concerted patterns of electronic flows in equilibrium states of the complementarily arranged substrates are investigated. Quantum communications between reactants are explored and the QIT descriptors of the A―B bond multiplicity/composition are extracted.

Electron donor–acceptor (D-A) tuning to achieve soluble covalent organic polymers for optoelectronic devices

Covalent organic polymers(COPs)have emerged as a unique class of luminescent polymers with pre-designed quasi-ordered architectures.However,their layered stacks and limited solubility preclude further processing for large-scale applications in devices,especially optoelectronic equipment.Herein,a universal strategy to adjust the electron donor–acceptor(D-A)moieties of the building blocks in COPs is proposed,achieved by in situ charge exfoliation of COP blocks into few-layer true solutions in(Lewis)acid and base media.The electron D-A moieties of the building blocks endow the COPs with the ability to accept or donate electrons,by altering the electron cloud distribution as well as the relative energy levels of the frontier molecular orbitals.The resultant soluble COPs can easily be processed into a uniform film by solution processing via the spin-coat method.The obtained COP-N achieves efficient and stable perovskite electroluminescence as a novel hole injection material on indium tin oxide,and the operating lifetime for a perovskite quantum dot light-emitting diodes device exceeds that of a poly(ethylene dioxythiophene):polystyrene sulphonate counterpart.This straightforward electronic regulation strategy provides a new avenue for the rational synthesis of processable reticular molecular polymers for practical electronic devices.

Donor-acceptor covalent organic frameworks-confined ultrafine bimetallic Pt-based nanoclusters for enhanced photocatalytic H_(2)generation

Photocatalytic hydrogen generation from hydrogen storage media is an effective and promising approach for the green hydrogen industry as well as for achieving carbon neutrality goals.However,the lower photocatalytic efficiency due to the limited light trapping capacity,low electron transfer rate,and severe aggregation of nanoparticles caused by high surface energy seriously restricts their practical application.Herein,we constructed a series of donor–acceptor(D–A)type covalent organic frameworks to confine ultrafine bimetallic Pt-based nanoclusters for photocatalytic hydrogen generation from ammonia borane(AB)hydrolysis.Under visible light irradiation at 20℃,PtCo_(2)@covalent organic framework(COF)showed the highest photocatalytic activity with a turnover frequency(TOF)of 486 min−1.Experiments and density functional theory(DFT)calculations reveal that the high catalytic activity is mainly attributed to the strong electronic interactions between D–A type COF and ultrafine PtCo_(2)nanoclusters.Specifically,the D–A type COF can significantly enhance the light-trapping ability by fine-tuning the electron-acceptor type in the framework,and accelerate the photogenerated electron transfer from D–A type COF to PtCo_(2)nanocluster,which promotes the adsorption and activation of H_(2)O and AB molecules and accelerates hydrogen release.Furthermore,PtCo_(2)@COF also exhibited ultra-high durability due to the significantly enhanced resistance to nanocluster aggregation caused by the nanopore confinement effect of D–A type COF.We believe that this work will provide a theoretical guide for the rational design of efficient D–A COFbased catalysts for photocatalysis.

Investigation on ab initio calculations of the electron donor-acceptor complex H_3N·SiH_3Cl and the hypervalence of Si in it

The formation and the presence of hypervalent Si in the electron donor-acceptor com- plex H_3N·SiH_3 Cl have been investigated by ab initio calculation. The results show that there is a 0.707eV decrease of energy when the complex H_3N.SiH_3 Cl is formed from NH_3 and H_3SiCl, the interaction potential between the donor NH_3 and the acceptor H_3SiCl belongs to the Morse type, and the bond angle A(H-Si-Cl) versus bond length d(N-Si) presents a linear relation. The results also show that the interaction is mainly from giving the lone pair electrons in HOMO of NH_3 to LUMO of H_3SiCl, in which the 2P_z of N and the 3d_0 of Si play important role. Bond N-Si is a weak n-σ*type dative one.

Embedding pyridine units in acceptors to construct donor-acceptor conjugated polymers

The development of donor-acceptor(D-A) conjugated polymers greatly promotes the device performance in organic electronics. Recently, the strategy of embedding pyridine units into D-A conjugated polymer backbones has attracted much attention due to the resulted lowered LUMO levels. In addition, the possible non-bonding interactions resulted from the nitrogen atoms also improve the coplanarity of the polymer backbones. All these factors have great contribution to enhance the device performance. In this review, we summarized the recent development of pyridine-embedded D-A conjugated polymers and their applications in organic field-effect transistors(OFETs).

Structure dependence of intramolecular photoinduced electron transfer in 9-aminoacridine benzoyl esters dyads linked by a polyether chain

ELECTRON transfer plays a crucial role in energy transformation of natural biological systemssuch as the photosynthetic process by which plants convert solar energy into chemical energy.This is achieved in photosynthesis by a series of electron transfers which occur after light is ab-sorbed. Among the various factors which influence the efficiency of electron transfer struc-tural effect is one of the important features to be considered. In recent years, numerous syn-thetic model dyads in which electron donor and electron acceptor are covalently linked by dif-ferent spacers have been designed and synthesized in an effort to understand how the

Electron transfer reaction of meso-phenyl-tetrabenzo-porphyrinato-zinc and dicyanobenzene at low temperature

The behavior of photon-gated spectral hole burning with meso-phenyl-tetrabenzoporphyrinato-zinc as electron donor and dicyanobenzene as electron acceptor dispersed in polymethylmethacrylate was investigated.The data of absorption spectrum of the photoproduct acquired through photon-gated hole burning process by high power density and long hole burning time at 20 K were given The mechanism of photomduced donor-acceptor electron transfer for the iarget system in photon-gated spectral hole burning was demonstrated.

In-situ transformed Mott-Schottky heterointerface in silver/manganese oxide nanorods boosting oxygen reduction,oxygen evolution,and hydrogen evolution reactions

The development of non-platinum group metal(non-PGM)and efficient multifunctional electrocatalysts for oxygen reduction reaction(ORR),oxygen evolution reaction(OER),and hydrogen evolution reaction(HER)with high activity and stability remains a great challenge.Herein,by in-situ transforming silver manganese composite oxide heterointerface into boosted Mott-Schottky heterointerface through a facile carbon reduction strategy,a nanorod-like silver/manganese oxide with superior multifunctional catalytic activities for ORR,OER and HER and stability was obtained.The nanorod-like silver/manganese oxide with Mott-Schottky heterointerface(designated as Ag/Mn_(3)O_(4))exhibits an ORR half-wave potential of 0.831 V(vs.RHE)in 0.1 M KOH,an OER overpotential of 338 mV and a HER overpotential of 177 mV at the current density of 10 mA·cm^(-2)in 1 M KOH,contributing to its noble-metal benchmarks comparable performance in aqueous aluminum-air(Al-air)battery and laboratorial overall water splitting electrolytic cell.Moreover,in-situ electrochemical Raman and synchrotron radiation spectroscopic measurements were conducted to further illustrate the catalytic mechanism of Ag/Mn_(3)O_(4)Mott-Schottky heterointerface towards various electrocatalytic reactions.At the heterointerface,the Ag phase serves as the electron donor and the active phase for ORR and HER,while the Mn_(3)O_(4)phase serves as the electron acceptor and the active phase for OER,respectively.This work deepens the understanding of the Mott-Schottky effect on electrocatalysis and fills in the gap in fundamental physical principles that are behind measured electrocatalytic activity,which offers substantial implications for the rational design of cost-effective multifunctional electrocatalysts with Mott-Schottky effect.

基于电子给体-受体复合物的脂肪烃碳氢键多样性转化

The ability to selectively introduce diverse functionality onto hydrocarbons is of substantial value in the synthesis of both small molecules and pharmaceuticals.In this endeavour,as a photocatalyst-and metalfree process,the electron donor–acceptor(EDA)strategy has not been well explored.Here we report an approach to aliphatic carbon-hydrogen bond diversification through an EDA complex constituted by HCl and S^(IV)=O groups.As an efficient hydrogen atom transfer(HAT)reagent,chlorine radical can be produced via a proton-coupled electron transfer process in this system.Based on this unusual path,a photopromoted versatile aliphatic C–H functionalization is developed without photo-and metal-catalysts,including thiolation,arylation,alkynylation,and allylation.This conversion has concise and ambient reaction conditions,good functional group tolerance,and substrate diversity,and provides an alternative solution for the high value-added utilization of bulk light alkanes.

Synthesis of Unprotectedα-Tertiary Amines and 1,2-Amino Alcohols from Vinyl Azides by Light Induced Denitrogenative Alkylarylation/Dialkylation

Sterically congestedα-tertiary primary amines are ubiquitous substructures in pharmaceutical and agrochemical agents yet are challenging to access.Herein,straightforward photoredox-catalyzed access to structurally diverseα,α,α-trisubstituted primary amines from denitrogenative alkylarylation or dialkylation of vinyl azides with N-hydroxyphthalimide(NHPI)esters and cyanoarenes or aryl aldehydes has been developed.The use of vinyl azide as a precursor to a primary aminewas enabled by the dual role of the Hantzsch ester to form an electron donor-acceptor complex and serve as a sacrificial reductant.This strategy provides a modular synthesis ofα-tertiary primary amines,including unprotected 1,2-amino alcohols,from simple materials with excellent functional group tolerance.The synthetic applicability of this method was demonstrated by streamlined access to 2,2-disubstituted tetrahydroquinolines.Preliminary investigations support two parallel reductive photocatalytic cycles allowing for the denitrogenative alkylarylation or dialkylation of vinyl azides via decarboxylative radical addition followed by heteroradical cross-coupling betweenα-amino radicals and aryl anion radicals or ketyl anion radicals.

Organic Semiconductor Interfaces and Their Effects in Organic Solar Cells

Energy levels and energy level alignment at interfaces play a decisive role in designing efficient and stable organic solar cells(OSCs).In this review two usually used technologies in organic photovoltaic communities for measuring energy levels of organic semiconductors,photoelectron spectroscopy and electrochemical methods,are introduced,and the relationships between the values obtained from the corresponding techniques are compared.The energy level and energy level alignment across the interfaces involved in solution processed organic photovoltaics are described,and the corresponding integer charge transfer model for predicting and explaining energy level alignment is presented.The effects of the interface properties in designing efficient binary and ternary OSCs were discussed.The effects of environmental factors mainly including water vapor,oxygen gas and thermal annealing on energy levels and energy level alignment involved in photoactive layers,and the subsequent effects on the corresponding OSC properties are given.

Oligo（p-phenyleneethynylene）-functionalized Perylenebis- imidetriad： Synthesis, Photophysical Properties, and Self-assembly

The rod-like oligo（p-phenylene ethynylene）-functionalized perylene bisimide triad was synthesized and characterized. Aggregation behavior in solvents of different polarity was investigated by absorption and fluorescent spectroscopy. The results showed that stronger aggregations took place in low-polarity slovent. The experiments also indicated that the energy and electron transfer might takeplace between the two chromophores during the photoinduced excitation. Highly ordered two-dimensional assemblies could be observed at solid/liquid interfaces.

n-Type Semiconductive Polymers Based on Pyrene-1,5,6,10-Tetracarboxyl Diimide

Donor-acceptor(D-A)conjugated polymers comprising electron-deficient aromatic dicarboximide units represent an important type of organic semiconductors,especially for electron transporting properties.Pyrene-1,5,6,10-tetracarboxyl diimide(PyDI),a new PAH dicarboximide molecule recently reported by us,provides a fine balance between the electron-stabilizing ability andπ-stacking tendency,as compared to the naphthalenediimide(NDI)and perylenediimide(PDI)analogues.In this study,using thienylene-vinylene-thienylene(TVT)and biselenophene(BS)as the electron donating comonomer,along with PyDI as the acceptor moiety,we develop two new D-A type conjugated polymers,which exhibit impressive electron-transporting performance.Specifically,in the solution-processed OFET devices,electron mobility of 0.18 and 0.20 cm^(2)·V^(−1)·s^(−1) are achieved with these polymers,respectively.Such findings further prove the optimal potential of PyDI for application as an electron-acceptor building block in the development of polymeric n-type semiconductors among all various high-performance functional D-A polymers.

Using unmodified Au nanoparticles as colorimetric probes for TNT based on their competitive reactions with melamine

Gold nanoparticles （Au NPs） can serve as visualized colorimetric probes for various targets and modification-free sensing strategies are preferred. The donor-acceptor interaction between the electron-rich melamine （MA） and the electron-deficient trinitrotoluene （TNT） allows formation of a supramolecule in aqueous solution. Melamine alone makes the initially individual reddish Au NPs aggregate into gray/blue Au NP assemblies due to melamine forming multiple ligand sites toward the Au NPs. Interestingly, the preformed supramolecule of MA-TNT disenables aggregation of the Au NPs. Therefore the unmodified Au NPs provide facile colorimetric probes for TNT detection in aqueous solution. Rapid identification of TNT is established by naked eye inspection. By using spectrophotometer tools, quantification of TNT is accomplished with a linear range of 80μmol L-1 to 1.2 mmol/L-1 and a limit of detection （LOD） of 27μmol/L^-1. In contrast to previous strategy with surface-modified Au NPs, here a modification-free sensing strategy for TNT assay has been developed with greater convenience, rapidity, and cost-effectiveness.

Visible-light-induced N-heterocyclic carbene mediated cascade transformation of N-alkenoxypyridinium salts

While N-alkenoxypyridinium salts are widely used for the synthesis ofα-functionalized ketones via umpolung strategy,such approaches are usually limited to special nucleophiles at high temperatures.Herein,we developed an alternative photoinduced N-heterocyclic carbene(NHC)-mediated functionalization of N-alkenoxypyridinium salts with various nucleophiles,including tetramethylammonium azide,secondary amines,aryl and alkyl thiols,and even the challenging C(sp^(3))-nucleophiles,under mild conditions.A cascade radical-radical coupling/nucleophilic substitution sequence was proposed,wherein the NHC enabled the formation of a photoactive electron donor-acceptor complex forα-iodo ketone synthesis.

Customizable 2D Covalent Organic Frameworks for Optoelec-tronic Applications

2D covalent organic framework(2D-COF),a modular three-dimensional material,is easily influenced by the component module.The assembly of different functionalized modules gives 2D-COF unique performance.The modular structure not only allows for customi-zation but also allows for variety,which gives 2D-COF a wide range of functions.Hence,many building blocks with catalytic,ligand,semiconductor,luminescent,and redox centers are integrated into the COF scaffold.The connection and assembly of such modules determine the nature of the final block material.The intra-layer connections of the modules form a monolayer mesh chemical structure,and the subsequent stacking of the monolayer mesh structure produces the final crystalline porous material-2D-COF.This review describes in detail the potential of COF materials as optoelectronic materials and our understanding of optoelectronic processes,starting from monolayer reticulation chemistry to final 3D stacked structures,thus establishing a new paradigm for the ra-tional design of well-defined novel 2D-COF optoelectronic materials and devices.