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91.
Fernández EJ Laguna A López-De-Luzuriaga JM Mendizabal F Monge M Olmos ME Pérez J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(2):456-465
The reactions of solutions of TlPF(6) and OPPh(3) in tetrahydrofuran or acetone with NBu(4)[AuR(2)] (R=C(6)Cl(5), C(6)F(5)) gave the new complexes [Au(C(6)Cl(5))(2)](2)[Tl(OPPh(3))][Tl(OPPh(3))(L)] (L=THF (1), acetone (2)) and the previously reported [Tl(OPPh(3))(2)][Au(C(6)F(5))(2)] (3). The crystal structures of complexes 1 and 2 display extended unsupported chains with short intermolecular interactions between alternating gold(I) and thallium(I) centres. Moreover, the Tl(I) centres show two different types of geometrical environments, such as pseudotetrahedral and distorted trigonal-bipyramidal, due to the presence of solvent molecules that act as ligands in the solid-state structure. Quasirelativistic and nonrelativistic ab initio calculations were performed to study the nature of the intermetallic Au(I)-Tl(I) interactions and are consistent with the presence of a high ionic contribution (80 %) and dispersion-type (van der Waals) interaction with a charge-transfer contribution (20 %) when relativistic effects are taken into account. All complexes are luminescent in the solid state at room temperature and at 77 K. Complexes 1 and 2 show site-selective excitation, probably due to the different environments around the Tl(I) centres. The DFT and time-dependent (TD)-DFT calculations are in agreement with the experimental excitation spectra for all complexes and confirm the site-selective excitation behaviour as a function of the Tl(I) geometrical environment. 相似文献
92.
Vânia H.J. Frade 《Tetrahedron letters》2007,48(19):3403-3407
3-(Naphthalen-1-ylamino)propanoic acid was coupled to the amino group of the main and lateral chains of various amino acids in order to evaluate its applicability as a fluorescent derivatising reagent. The resulting amino acid derivatives are strongly fluorescent with a maximum emission of about 415 nm. Condensation of these derivatives with 5-ethylamino-4-methyl-2-nitrosophenol hydrochloride resulted in the corresponding blue benzo[a]phenoxazinium conjugates, also revealing strong fluorescence in ethanol and water at physiological pH and good quantum yields, but with emission wavelengths between 644 and 657 nm, which was preferable in biological assays. 相似文献
93.
J.W.H. van KrevelJ.W.T. van Rutten H. MandalH.T. Hintzen R. Metselaar 《Journal of solid state chemistry》2002,165(1):19-24
New interesting luminescent α-sialon (M(m/val+)val+ Si12-(m+n) Al(m+n)OnN(16−n)) (M=Ca, Y) materials doped with Ce, Tb, or Eu have been prepared and their luminescence properties studied. These show that Tb and Ce are in the 3+ and Eu in the 2+ state. Low-energy 4f↔5d transitions are observed as compared to the luminescence of these ions doped in oxidic host-lattices. This is partially explained by the nitrogen-rich coordination of the rare-earth ion and partially by the narrow size of the lattice site. The latter gives rise to a strong crystal-field splitting of the 5d band and a rather large Stokes shift for Ce3+ and Eu2+ (6500-7500 and 7000-8000 cm−1, respectively). For (Y,Tb)-α-sialon the Tb3+ 4f→5d excitation band (∼260 nm) is in the low-energy host-lattice absorption band (?290 nm), giving rise to a strong absorption for 254-nm excitation, but a low quantum efficiency. The latter is due to photoionization processes or selective excitation of Tb3+ at the defect-rich surface, resulting in radiationless transitions. Ce- and Eu-doped Ca-α-sialon show bright long-wavelength luminescence (maxima at 515-540 and 560-580 nm for Ce and Eu, respectively) with a high quantum efficiency and high absorption for 365- and 254-nm excitation. The Eu2+ emission intensity and absorption increases for increasing m, which is explained by the Eu2+ richer α-sialon composition. The position of the Eu2α emission does not shift with changing composition of the host-lattice (m, n values), indicating that the local coordination of the Eu2+ ion is hardly dependent on the matrix composition. 相似文献
94.
Klärner FG Kahlert B Boese R Bläser D Juris A Marchioni F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(11):3363-3374
Novel molecular clips with anthracene sidewalls (1 a-c) were synthesized; they form stable host-guest complexes with a variety of electron-deficient aromatic and quinoid molecules. According to single-crystal structure analyses of clip 1 c and 1,2,4,5-tetracyanobenzene (TCNB) complex 14@1 b, the clips' anthracene sidewalls have to be compressed substantially during the complex formation to provide attractive pi-pi interactions between the aromatic guest molecule and the two anthracene sidewalls in the complex. The compression and expansion of aromatic sidewalls are calculated by molecular mechanics to be low-energy processes, so the energy required for compression of the anthracene sidewalls during complex formation is apparently overcompensated by the gain in energy resulting from the attractive pi-pi interactions. The finding that complexes of the clips 1 a-c are more stable than those of the corresponding clips 2 a-c can be explained in terms of the larger van der Waals contact surfaces of the anthracene sidewalls in 1 a-c (relative to the naphthalene sidewalls in 2 a-c). Color changes resulting from charge-transfer (CT) bands are observed in complex formation by 1 a-c: from colorless to red or purple with TCNB (14), and from yellow to green with 2,4,7-trinitro-9-fluorenone TNF (17). Independently, the host 1 b and guest 14 fluoresce from their respective excited singlet states, whilst in the complex 14@1 b the charge-transfer state quenches the higher-energy singlet states of the two components, and as a result luminescence is only observed from this new CT state. To the best of our knowledge, complex 14@1 b is the first example of CT luminescence from a host-guest complex. The binding constant determined for the formation of the TCNB complex 14@1 b from a UV/Vis titration experiment (Ka = 12 400 m(-1)) agrees well with the value (K(a) = 12 800 m(-1)) obtained by 1H NMR titration. 相似文献
95.
Pradip K. Bhowmik Haesook Han James J. Cebe Ronald A. Burchett Ananda M. Sarker 《Journal of polymer science. Part A, Polymer chemistry》2002,40(5):659-674
A series of viologen polymers with bromide, tosylate, and triflimide as counterions were prepared by either the Menshutkin reaction or metathesis reaction in a common organic solvent. Their polyelectrolyte behavior in methanol was determined by solution viscosity measurements, and their chemical structures were determined by Fourier transform infrared and Fourier transform NMR spectroscopy. They were characterized for their thermotropic liquid‐crystalline properties with a number of experimental techniques. Each of the viologen polymers with organic counterions had a low melting transition or fusion temperature above which it formed either a high‐order smectic phase or a low‐order smectic phase. Each of them also exhibited a smectic‐to‐isotropic transition. The ranges of the liquid‐crystalline phase were 80–88 °C for viologen polymers with tosylate as a counterion and 120–146 °C for viologen polymers with triflimide as a counterion. They had excellent thermal stability. The ranges of thermal stability were 288–329 °C for viologen polymers with tosylate as a counterion and 343–350 °C for viologen polymers with triflimide as a counterion. The fluorescence property for all of the viologen polymers in either aqueous or methanol solution was also included in this study. For example, the viologen polymer containing the 4,4′‐bipyridinium and p‐xylyl units along the backbone of the polymer chain with triflimide as a counterion had an absorption spectrum (λmax = 265 nm), an excitation spectrum (λex values = 357, 443, and 454 with monitoring at 533 nm), and an emission spectrum (λem = 536 nm with excitation at 430 and 450 nm) in methanol. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 659–674, 2002; DOI 10.1002/pola.10134 相似文献
96.
Lainé PP Ciofini I Ochsenbein P Amouyal E Adamo C Bedioui F 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(12):3711-3727
As an alternative to conventional charge-separation functional molecular models based on long-range ET within redox cascades, a "compact approach" has been examined. To this end, spacer elements usually inserted between main redox-active units within polyad systems have been removed, allowing extended rigidity but at the expense of enhanced intercomponent electronic communication. The molecular assemblies investigated here are of the P-(theta (1))-A type, where the theta (1) twist angle is related to the degree of conjugation between the photosensitizer (P, of {Ru(bpy)(3)}(2+) type) and the electron-acceptor (A). 4-N- and 4-N-,4'-N-(2,4,6-triphenylpyridinio)-2,2'-bipyridine ligands (A(1)-bpy and A(2)-bpy, respectively) have been synthesized to give complexes with Ru(II), 1-bpy and 2-bpy, respectively. Combined solid-state analysis (X-ray crystallography), solution studies ((1)H NMR, cyclic voltammetry) and computational structural optimization allowed verifying that theta (1) angle approaches 90 degrees within 1-bpy and 2-bpy in solution. Also, anticipated existence of strong intercomponent electronic coupling has been confirmed by investigating electronic absorption properties and electrochemical behavior of the compounds. The capability of 1-bpy and 2-bpy to undergo PET process was evaluated by carrying out their photophysical study (steady state emission and time-resolved spectroscopy at both 293 and 77 K). The conformational dependence of photoinduced processes within P-(theta (1))-A systems has been established by comparing the photophysical properties of 1-bpy (and 2-bpy) with those of an affiliated species reported in the literature, 1-phen. A complementary theoretical analysis (DFT) of the change of spin density distribution within model [1-bpy(theta (1))](-) mono-reduced species as a function of theta (1) has been undertaken and the possibility of conformationally switching emission properties of P was derived. 相似文献
97.
98.
The silver-dppm complex, [Ag2(dppm)2(NMP)2](SbF6)2·4H2O·3CH2Cl2 1 (NMP = 2- (4-dimethylaminophenyl)imidazo(4,5-f)(1,10)phenanthroline, dppm = diphenylphosphinomethane), was synthesized and its structure was determined by X-ray diffraction. The crystal belongs to mono- clinic, space group C2/c, Mr = 2461.61, a = 21.57(10), b = 22.48(6), c = 22.53(6) (A), β = 101.29(2)o, V = 10713(64) (A)3, Z = 4, Dc = 1.526 g/cm3, μ = 1.141 mm-1, F(000) = 4920, R = 0.0664 and Wr = 0.1774 for 8524 observed reflections (I > 2σ(I)). Complex 1 exists as a centrosymmetric dimmer. The two dppm molecules bridge two AgNMP moieties to form an eight-membered Ag2P4C2 metal- lacyclic ring with ligand NMP chelating to each Ag. It appears photoluminescence λ(max = 625 nm) at room temperature and makes red shift compared with free ligand NMP λ(max = 522 nm). DFT calculation indicates that the emission of 1 originates from singlet metal-perturbed ILCT excited state. 相似文献
99.
The syntheses and the X-ray structures of the tetranuclear gold(I) benzamidinate, Au4[PhNC(Ph)NPh]4, and the tetranuclear gold(I) acetamidinate, Au4[PhNC(CH3)NPh]4, clusters are reported. The clusters are produced by the reaction of the sodium salt of an amidine ligand with the gold precursor
Au(THT)Cl in a (1:1) stoichiometry. The average Au...Au distance between adjacent Au(I) atoms is ∼2.9 ?, typical of compounds
having an aurophilic interaction. The four gold atoms are arranged in a square (Au...Au...Au... = 88–91°) in the acetamidinate
and in a distorted square (Au...Au...Au... = 82–97°) in the benzamidinate derivative. Electrochemical oxidation of the tetranuclear
complex Au4[PhNC(Ph)NPh]4 show three reversible waves at 0.87, 1.19, 1.42 V vs. Ag/AgCl at a scan rate of 100 mV/s in CH2Cl2 similar to the three reversible waves seen before from the tetranuclear complexes Au4[ArNC(H)NAr]4, Ar = C6H4-4-OMe, Ar = C6H4-4-Me, and Ar = C6H3-3,5-Cl. A summary of the chemistry of the tetranuclear Au(I) amidinate complexes Au4[ArNC(H)NAr]4, Ar = C6H4-4-OMe, C6H3-3,5-Cl, C6H4-4-Me, C6H4-3-CF3, C6F5, C10H7 also is presented. The tetranuclear clusters Au4[ArNC(H)NAr]4, Ar = C6H4-4-OMe, Ar = C6H4-3-CF3, Ar = C6H4-4-Me and Ar = C6H4-3,5-Cl are the first tetranuclear gold(I) cluster species from group 11 elements to show fluorescence at room temperature.
The lifetimes of the naphthyl and trifluoromethylphenyl complexes are in the millisecond range indicating phosphorescent processes.
Recently it has been shown that Au4[ArNC(H)NAr]4 are very effective catalysts upon calcination for room temperature CO oxidation.
Congratulations to Dieter Fenske, a superb synthetic chemist with exceptional talents in cluster chemistry, on the occasion
of his 65th birthday. 相似文献
100.
近十几年来,对小分子过渡金属配合物与大分子DNA键合与识别机理的研究一直是国际上生物无机化学领域十分活跃的研究课题[1 ̄3],已发展了一系列具有特定功能的配合物,如DNA结构探针和DNA荧光探针等。与其他类型的金属配合物相比,八面体过渡金属多吡啶配合物具有丰富的光化学和光物理信息,当这些配合物与DNA相互作用时,由于结构匹配或微环境的差异,配合物的光谱特征会出现不同程度的改变,从而达到对DNA的检测。传统的DNA荧光探针有[Ru(bpy)2dppz]2 和[Ru(phen)2dppz]2 (bpy=2,2′-联吡啶,phen=1,10-菲咯啉,dppz=二吡啶[3,2-a∶2′,3′… 相似文献