Electron Momentum Spectroscopy of Valence Orbitals of n-Propyl Iodide： Spin-Orbit Coupling Effect and Intramolecular Orbital Interaction

The binding energy spectrum and electron momentum distributions for the outer valence orbitals of n-propyl iodide molecule have been measured using the electron momentum spectrometer employing non-coplanar asymmetric geometry at impact energy of 2.5 keV plus binding energy. The ionization bands have been assigned in detail via the high accuracy SACCI general-R method calculation and the experimental momentum profiles are compared with the theoretical ones calculated by Hartree-Fock and B3LYP/aug-cc-pVTZ（C,H）6-311G？？（I）. The spin-orbit coupling effect and intramolecular orbital interaction have been analyzed for the outermost two bands, which are assigned to the iodine 5p lone pairs, using NBO method and non-relativistic as well as relativistic calculations. It is found that both of the interactions will lead to the observed differences in electron momentum distributions. The experimental results agree with the relativistic theoretical momentum profiles, indicating that the spin-orbit coupling effect dominates in n-propyl iodide molecule.

THE INTRAMOLECULAR AROMATIC-RING STACKING INTERACTION OF MIXED LIGAND PALLADIUM(Ⅱ)COMPLEXES Ⅲ.STUDIES ON THE Pd^(2+)-A-UTP^(4-)SYSTEMS BY HNMR

The intramolecular aromatic-ring stacking interaction of mixed- ligand complex Pd(A)(UTP)^(2-)in the system pd^(2+)-A-UTP^(4-)has been determined by ~1HNMR,where A=1,10-phenanthroline(phen),2,2'-bipyridyl(bpy)and DL- tryptophan(trp^-);UTP^(4-)=uridine 5-triphosphate.The result indicates that it is the partial stacking between the uracil ring of UTP^(4-)and the heterocyclic ring of A that makes H(5),H(6)and H(1')in the UTP^(4-)shift upfield signifi- cantly.Accordingly,the order of aromatic-ring interaction in the mixed- ligand complex has been obtained as follows:Pd(phen)(UTP)^(2-)(?)Pd(bpy)(UTP)^(2-) Pd(trp)(UTP)^(3-).

Luminescent properties of thermally activated delayed fluorescence molecule with intramolecular π-π interaction between donor and acceptor

Influence of intramolecular π-π interaction on the luminescent properties of thermally activated delayed fluorescence（TADF） molecule（3, 5-bis（3,6-di-tert-butyl-9 H-carbazol-9-yl）-phenyl）（pyridin-4-yl） methanone（DTCBPY） is theoretically studied by using the density functional theory（DFT） and time-dependent density functional theory（TD-DFT）.Four conformations（named as A, B, C, and D） of the DTCBPY can be found by relax scanning, and the configuration C corresponds to the luminescent molecule detected experimentally. Besides, we calculate the proportion of each conformation by Boltzmann distribution, high configuration ratios（44% and 52%） can be found for C and D. Moreover, C and D are found to exist with an intramolecular π-π interaction between one donor and the acceptor; the intramolecular interaction brings a smaller Huang-Rhys factor and reduced reorganization energy. Our work presents a rational explanation for the experimental results and demonstrates the importance of the intramolecular π-π interaction to the photophysical properties of TADF molecules.

Energy decomposition analysis for intramolecular non-covalent interaction in solvated environment

In this work, the intra-EDA method, which is a recently developed energy decomposition analysis scheme for intramolecular non-covalent interaction is extended from gas phase to solvated environment. It is the first analysis scheme that performs analysis for intramolecular interaction in solution. By fragmentation scheme, a molecule is divided into intramolecular interacting fragments and environmental fragments via single bond homolysis breaking. The solvent effect is taken into account by implicit solvation model. Intramolecular interaction free energy is estimated as the separated treatment of inter-fragment interactions in dielectric environment. The analysis results highlight the importance of solvent effects to intramolecular non-covalent interaction.

NBS-LRR Proteins and Their Partners:Molecular Switches of Plant Defense

Specificity of the plant innate immune system is often conferred by resistance（R）proteins.Most plant disease resistance （R）proteins contain a series of leucine-rich repeats（LRRs）,a nucleotide-binding site（NBS）,and a putative amino-terminal signaling domain.They are termed NBS-LRR proteins.The LRRs are mainly involved in recognition,and the amino-terminal domain determines signaling specificity,whereas the NBS domain presumably functions as a molecular switch.During the past years,the most important discoveries are the role of partners in NBS-LRR gene mediated defenses,mounting support for the so-called＂guard hypothesis＂of R gene function,and providing evidence for intramolecular interactions and intermolecular interactions within NBS- LRR proteins as a mode of signaling regulation.The outcome of these interactions determines whether a plant activates its defense responses.

Recent progress in non-fused ring electron acceptors for high performance organic solar cells

In recent years,significant progress has been witnessed in organic solar cells(OSCs),which is mainly attributed to the new active layer materials design,especially fused ring acceptors.However,the majority of fused-ring acceptors suffer from complicated synthetic procedures and unsatisfactory reaction yields and thus high preparation cost.It is difficult to reconcile with the necessity for OPVs to demonstrate the low cost advantage compared with other photovoltaic technologies such as silicon or perovskite solar cells,thus significantly limiting the future application of OSCs.Therefore,it is necessary to develop high efficiency but low cost acceptor materials,i.e.non-fused ring electron acceptors(NFREAs).In this review,the recent development of NFREAs from the viewpoint of materials design is discussed.In the first and second sections,NFREAs with different central cores are reviewed.Then,the progress of fully non-fused NFREAs is summarized.Finally,an outlook on the remaining challenges to the field is provided.

Conformation preference and related intramolecular noncovalent interaction of selected short chain chlorinated paraffins

Short chain chlorinated paraffins （SCCPs） are not only research focus of environmental issues but also interesting model mol- ecules for organic chemistry which exhibit diverse conformation preference and intramolecular noncovalent interactions （NCIs）. A systematic study was conducted to reveal the conlk）rmation preference and the related intramolecular NCIs in two C^-isomers of SCCPs, 5,5,6,6-tetrachlorodecane and 4,4,6,6-1etrachlorodecane. The overall conformation profile was deter- mined on the basis of relative energies calculated at the MP2/6-311＋＋G（d,p） level with the geometries optimized by B3LYP/6-31 l＋＋G（d,p） method. Then, quantum theory of atoms in molecules （QTAIM） has been adopted to identify the NCls in the selected conformers of the model molecules at both B31~YP/6-31 l＋＋G（d,p） and M06-2X/aug-cc-pvdz level. Different chlorine substitution modes result in varied conformation preference. No obvious gauche effect can be observed tk）r the SCCPs with chlorination on adjacent carbon atoms. The most stable conformer of 5,5,6,6-tetrachlorodecane （tTt） has its three dihedral angles in the T configuration, and there is no intramolecular N（3s found in this molecule. On the contrary, the chlorination on interval carbon atoms favors the adoption of gauche configmation for the H C C CI axis. Not only inlramolecular H-..CI contacts but also H---H interactions have been identified as driving forces to compensate the instability from steric crowding ot the gauche configuration. The gggg and g＇g＇g＇g＇ conformers are the most popular ones, while the populations of tggg and tg＇g＇g＇ conformer are second to those of the gggg and g＇g＇g＇g＇ conformers. Meanwhile, the M06-2X method with large basis sets is preferred for identification of subtle intramolecular NCIs in large molecules like SCCPs.

Stable Quadruple Helical Tetraradicaloid with Thermally Induced Intramolecular Magnetic Switching

We report an air-stable tetraradicaloid based on a rarely explored perylenequinonoid(PQ)core,namely,tetrabenzo-annulated tetracyclopenta[b,e,k,n]perylene(TBCP),which has a quadruple helical structure.As validated by X-ray crystallographic analysis and theoretical calculations,the nonplanar TBCP possesses unique hybrid resonance structures of two open-shell singlet diradicaloids.Remarkably,magnetic measurements reveal that TBCP in powder form shows unusual magnetic hysteresis upon heating followed by cooling,corresponding to interconversion of structure isomers with different magnetic properties.Such electronic properties can be rationalized as the response of structural changes to external thermal stimuli,accompanied by a subtle balance of two types of intramolecular magnetic interactions between four-site spin centers.The results provide a novel organic polyradicaloid as an unprecedented example of a functional material with the potential for intramolecular magnetic switching.

Orthologous genesPm12andPm21from twowild relatives of wheat show evolutionary conservation but divergent powdery mildew resistance

Wheat powdery mildew,caused by Blumeria graminis f.sp.tritici(Bgt),is a devastating disease that threatens wheat production worldwide.Pm12,which originated from Aegilops speltoides,a wild relative of wheat,confers strong resistance to powdery mildew and therefore has potential use in wheat breeding.Using susceptible mutants induced by gamma irradiation,we physically mapped and isolated Pm12 and showed it to be orthologous to Pm21 from Dasypyrum villosum,also a wild relative of wheat.The resistance function of Pm12 was validated via ethyl methanesulfonatemutagenesis,virus-induced gene silencing,and stable genetic transformation.Evolutionary analysis indicates that the Pm12/Pm21 loci in wheat species are relatively conserved but dynamic.Here,we demonstrated that the two orthologous genes,Pm12 and Pm21,possess differential resistance against the same set of Bgt isolates.Overexpression of the coiledcoil domains of both PM12 and PM21 induces cell death in Nicotiana benthamiana leaves.However,their full-length forms display different cell death-inducing activities caused by their distinct intramolecular interactions.Cloning of Pm12 will facilitate its application in wheat breeding programs.This study also gives new insight into two orthologous resistance genes,Pm12 and Pm21,which show different race specificities and intramolecular interaction patterns.

Synthesis, spectroscopic, and electrochemical properties of two dyads consisted of tetrathiafulvalene and carbazole

Two donor-σ-acceptor molecules containing tetrathiafulvalene(TTF)and carbazole moieties were synthesized bythe reactionof 9-(4-bromo-butyl)-carbazole(1)with 2,6-bis(hexylthio)-3-(2-cyanoethylthio)-7-(methylthio)-tetrathiafulvalene(2)or2,6-bis(2-cyanoethylthio)-3,7-bis(methylthio)tetrathiafulvalene(3)in the presence of CsOH·H_(2)O,respectively.The structures of the molecules were characterized by 1 H NMR,13 C NMR,MS,and elemental analyses.They showed negligible intramolecu-lar charge-transfer interaction in their ground states as indicated by their UV-Vis spectroscopics and cyclic voltammetry results.Compared with carbazole,their fluorescence was strongly quenched,which implied that a photo induced electron transfer(PET)interaction between TTF and carbazole moieties occurred.

High-Efficiency and Low-Energy-Loss Organic Solar Cells Enabled by Tuning Conformations of Dimeric Electron Acceptors

Dimeric fused-ring electron acceptors(DFREAs)have attracted much attention due to the combined advantages of their monomeric and polymeric acceptors,including a well-defined molecular structure,excellent repeatability,and stable morphology.However,the additionally introduced single-bonds during dimerization may result in a twisted backbone of DFREAs,which is detrimental to intermolecular packing and charge transport.Herein,three DFREAs are designed and synthesized,in which DFREA conformations were systematically tuned via adjusting the intensities of intramolecular noncovalent interactions(INIs)to achieve high-performance organic solar cells(OSCs).Theoretical and experimental results show that the gradual introduction of S…F INIs can continuously improve molecular planarity and rigidity,resulting in reduced reorganization energies,ordered packing mode,and enhanced crystallization of DFREAs.Benefiting from the incorporation of fourfold S…F INIs,DYF-TF-based binary OSCs show a record high efficiency of 18.26%with an extremely low energy loss(0.493 eV)for DFREAbased OSCs.In addition,DYF-TF-based OSCs exhibited good long-term stability with a T_(80%)lifetime of 2681 h,and the power conversion efficiency of the DYF-TF-based ternary device is further enhanced to 18.73%.This contribution demonstrates the great potential of the INIs strategy in achieving excellent DFREAs materials.