Organogelators based on TTF supramolecular assemblies: synthesis, characterization, and conductive property

A closely related family of organogelators 1-2 appended one or two electroactive tetrathiafulvalene (TTF) residues, has been designed and readily synthesized by Sonogashira reactions. These compounds can gelate a variety of organic solvents in view of multiple intermolecular interactions, and compounds 2 with two TTF subunits exhibit higher gelation ability than their corresponding 1. Scanning electron microscopy (SEM) and transmission electron microscopy (TEM) investigation of the xerogels from toluene gave a visual image showing that fibrillar aggregates are entangled in three-dimensional network structures. The columnar TTF cores stacking in the fiber, evidenced by the mixed-valence states absorption at around 2000 nm in ultraviolet-visible-near-infrared (UV-vis-NIR) spectra, provide an efficient pathway for the electron conduction. Upon oxidized by iodine, these xerogels exhibit semiconductive behaviors with moderate levels of conductivity. Additionally, the electrical conductivity of doped-xerogels 2 is 1 order of magnitude higher than that of 1 under identical conditions.     

左手介质对谐振腔谐振频率的影响

在谐振腔设计过程中, 谐振腔的品质因数以及谐振频率都是需要考虑的关键因素. 传统的方法是通过减小谐振腔的尺寸或者利用高次模来提高谐振腔的谐振频率, 但是由于两种方法都有其局限性, 导致设计结果并不理想. 通过理论计算与模拟仿真相结合的方法, 对影响谐振腔谐振频率的因素进行分析, 得出了填充介质的材料属性与谐振腔谐振频率的关系. 理论计算显示: 当用“左手介质”作为谐振腔的填充物质时, 可以在不改变谐振腔尺寸的基础上提高谐振频率. 高频结构仿真器(high frequency structure simulator)的仿真数据也证明了以上结果, 从而得出谐振腔的谐振频率可以不受谐振腔尺寸的限制. 相较于传统理论而言, 研究结论有进一步的发展, 为探索和设计新颖的谐振腔提供了理论依据.     

Stiff-stilbene derivatives as new bright fluorophores with aggregation-induced emission

Stiff-stilbene derivatives have been widely explored as molecular rotors, molecular force probes and optical switches with excellent performance. However, their function as fluorophores is poorly understood. In the present work, we design three stiffstilbene derivatives and study their photophysical properties. These compounds exhibit very weak emission in solution but significantly enhanced monomer emission in viscous solvent, bright excimer emission in aggregates and at solid state. Detailed spectroscopic studies, single crystal structural analysis, powder X-ray diffraction(XRD) as well as effects of substituents have been carefully examined. They provide direct evidence that intermolecular interactions and molecular packing, which can restrict bond vibration and rotation, are responsible for the bright aggregation-induced emission.     

高温超导氧化物中非平衡载流子的能量弛豫与电声相互作用

利用超导体中非平衡能量平衡模型,研究室温下YBa₂Cu₃O_7-δ(δ=0.1,0.4,0.8)和PrBa₂Cu₃O₇外延膜中光激活非平衡载流子的弛豫动力学,计算了电声耦合常数λ发现随着氧含量的降低及用Pr替代Y,Cu-O面上空穴Fermi面向Cud⁹/d¹⁰带方向移动,非平衡载流子的驰豫时问增加而电声耦合常数明显减小.这一结果与瞬态反射谱测量结果符合得很好.这表明载流子浓度的降低减弱了电声相互作用,而这种作用可能是一种实空间的局域相互作用.     

Photosensitized oxidative deprotection of oximes to their corresponding carbonyl compounds by platinum(II) terpyridyl acetylide complex

Platinum(II) terpyridyl acetylide complex (1) photosensitizes the oxidation of aldoximes 2-4, aliphatic acyclic and cyclic ketoximes 5-7, and aromatic ketoximes 8-10 into their corresponding carbonyl compounds with good to excellent yields in acetonitrile solution. This deprotection of oximes proceeds via singlet oxygen ((1)O(2)) mechanism. The photosensitizer can be easily separated from the product and unreacted starting material by extraction with ethyl acetate and reused for photooxidation without loss of (1)O(2)-generation capacity.     

Enantioselectivity of Photochemical Reactions within Polymer Microcapsules

Polymer microcapsule was employed as a reactionmedium to achieve enantioselectivity in photochemical reduction of phenyl cyclohexyl ketone and photoelectrocycliztion of tropolone methyl ether under the influence of various chiral inductors.In all cases,low but evident enantioselectivity was observed.The poor enantioselectivity is probably due to the facts that not all the capsules include simultaneously both the chiral inductor and the reactant molecules,and the wall of the microcapsule is not rigid enough to hold the reactant and the chiral inductor molecules in close contact.     

Nanosized particles of organically modified silica as microreactors to enhance the regioselectivity in the photocycloaddition of 9-substituted anthracenes

[reaction: see text] Nanosized particles of modified silica with 3-ammoniumpropyl residue have been prepared and successfully used as microreactors to control the regioselectivity of the photocycloaddition of five 9-substituted anthracences [AnCH(2)N(+)(CH(3))(3)Br(-) (1), AnCH(2)COO(-)Na(+) (2), AnCH(2)CH(2)COOH (3), AnCH(2)OH (4), AnCH(3) (5), where An = 9-anthryl]. While the photocycloaddition of the five substrates in methanol mainly gave rise to their head-to-tail (h-t) photocyclomers, irradiation of 1-4 incorporated in the suspension of the modified silica in methanol almost exclusively yielded the head-to-head (h-h) photocyclomers with high quantum yields.     

Zipper-featured delta-peptide foldamers driven by donor--acceptor interaction. Design, synthesis, and characterization

Donor-acceptor interaction between electron-rich 1,5-dioxynaphthalene (DAN) and electron-deficient pyromellitic diimide (PDI) has been utilized to induce the formation of a new kind of zipper-featured delta-peptide foldamers. Seven l-ornithine-based delta-peptides 1a-g, in which one to three DNA and PDI units are incorporated to the two ends of the peptide backbones, respectively, have been designed and prepared by the standard liquid-phase synthetic method. (1)H NMR, UV-vis, and fluorescent quenching studies reveal that all the delta-peptides adopt folding conformations in nonpolar chloroform and polar DMF as a result of intramolecular donor-acceptor interaction between the DAN and PDI units. The folding states become more compact for the peptide skeletons possessing more donor-acceptor interacting sites. Variable-temperature UV-vis experiments indicate that, although the folding is a dynamic process, the folding state can remain even at 150 degrees C in DMF. Circular dichroism (CD) investigations reveal that the new generation of delta-peptides have similar folding patterns. A zipper-featured folding motif has been proposed for the new generation of delta-peptide foldamers. Molecular modeling has generated two most stable folding states for the longest delta-peptide 1g, with an energy difference of 26.80 kcal/mol.     

Enhanced stereoselectivity in photoelectrocyclization of tropolone ethers via confinement in chiral inductor-modified lyotropic liquid crystals

Photochemistry of tropolone methyl ether ( 1) and optically pure ( S)-tropolone-2-methylbutyl ether ( 4) has been examined in lyotropic liquid crystals (LCs) in the presence of a chiral inductor. LCs significantly enhance the influence of chiral inductors during the photoelectrocyclization of the tropolone ethers. Chiral inductors that lead to 1:1 mixtures of enantiomers or diastereomers in solution give products in up to 40% enantiomeric excess for 1 and 35% diastereomeric excess for 4 in LCs.     

Switching between ligand-to-ligand charge-transfer, intraligand charge-transfer, and metal-to-ligand charge-transfer excited states in platinum(II) terpyridyl acetylide complexes induced by pH change and metal ions

A series of platinum(II) terpyridyl alkynyl complexes, [Pt{4'-(4-R1-C6H4)terpy}(C[triple chemical bond]C-C6H4-R(2)-4)]ClO4 (terpy=2,2':6',2'-terpyridyl; R1=R2=N(CH3)2 (1); R1=N(CH3)2, R2=N-[15]monoazacrown-5 (2); R1=CH3, R2=N(CH3)2 (3); R1=N(CH3)2, R2=H (4); R1=CH3, R2=H (5)), has been synthesized and the photophysical properties of the complexes have been examined through measurement of their UV/Vis absorption spectra, photoluminescence spectra, and transient absorptions. Complex 3 shows a lowest-energy absorption corresponding to a ligand-to-ligand charge-transfer (LLCT) transition from the acetylide to the terpyridyl ligand, whereas 4 shows an intraligand charge-transfer (ILCT) transition from the pi orbital of the 4'-phenyl group to the pi* orbital of the terpyridyl. Upon protonation of the amino groups in 3 and 4, their lowest-energy excited states are switched to dpi(Pt)-->pi*(terpy) metal-to-ligand charge-transfer (MLCT) states. The lowest-energy absorption for 1 and 2 may be attributed to an LLCT transition from the acetylide to the terpyridyl. Upon addition of an acid to a solution of 1 or 2, the amino group on the acetylide is protonated first, followed by the amino group on the terpyridyl. Thus, the lowest excited state of 1 and 2 can be successively switched from the LLCT state to the ILCT state and then to the MLCT state by controlling the amount of the acid added. Such switches in the excited state are fully reversible upon subsequent addition of a base to the solution. Sequential addition of alkali metal or alkaline earth metal ions and then an acid to a solution of 2 also leads to switching of its lowest excited state from the LLCT state, first to the ILCT state and then to the MLCT state. All of the complexes exhibit a transient absorption of the terpyridyl anion radical, which is present in all of the LLCT, ILCT, and MLCT states. However, the shape of the transient absorption spectrum depends on both the substitution pattern on the terpyridyl moiety and the nature of the excited state.