Theoretical Studies on Structures and Spectroscopic Properties of Highly Efficient Phosphorescent [Ru（terpy）（phen）X]＋ Complexes

The ground and the lowest-lying triplet excited state geometries, electronic structures, and spectroscopic properties of three mixed-ligand Ru（II） complexes [Ru（terpy）（phen）X]＋ （terpy=2,2＇,6＇,2″-terpyridine, phen=l,10-phenanthroline, and X=-C-=CH （1）, X=Cl （2）, X-CN （3）） were investigated theoretically using the density functional theory method. The ground and excited state geometries have been fully optimized at the B3LYP/LanL2DZ and UB3LYP/LanL2DZ levels, respectively. The absorption and emission spectra of the com- plexes in CHaCN solutions were calculated by time-dependent density functional theory with the PCM solvent model. The calculated bond lengths of Ru-C, Ru-N, and Ru-Cl in the ground state agree well with the corresponding experimental results. The highest occupied molecular orbital were dominantly localized on the Ru atom and monodentate X ligand for 1 and 2, Ru atom and terpy ligand for a, while the lowest unoccupied molecular orbital were π＊（terpy） type orbital. Therefore, the lowest-energy absorptions of 1 and 2 at 688 and 631 nln are attributed to a dyz （Ru）＋Tr/p（X）--π＊ （terpy） transition with MLCT/XLCT （metal-to-ligand charge transfer/X ligand to terpy ligand charge transfer） character, whereas that of 3 at 529 nm is related to a dyz （Ru）＋π（terpy）-π＊ （terpy） transition with MLCT and ILCT transition character. The calculated phosphorescence of three complexes at 1011 nm （1）, 913 nm （2）, and 838 nm （3） have similar transition properties to that of the lowest-lying absorption. It is shown that the lowest lying absorptions and emissions transition character of these Ru（II） complexes can be tuned by changing the electron-withdrawing ability of the monodentate ligand.

Ionic palladium complex as an efficient and recyclable catalyst for the carbonylative Sonogashira reaction

The neutral palladium（Ⅱ） complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-imidazolyl]dichloropalladium（Ⅱ）（1A） ligated by thiazolylimidazolyl-based phosphine（L1） in which thiazolylimidazolyl acted as an S- and N-donor provider with weak coordinating nature,and the ionic complex bis-[1-（5＇-diphenylphosphinothiazol-2＇-yl）-3-methylimidazolium]dichloropalladium（Ⅱ） trifluoromethanesulfonate（2A） ligated by thiazolylimidazolium-based phosphine（L2） after quaternization of L1 using methyl trifluoromethanesulphonate were synthesized.It was found that the introduced positive charges and strong electron-withdrawing effect in 2A not only led to changes in the configuration and structural stability of the complex,but also lowered its catalytic performance in carbonylative Sonogashira reactions.These effects reveal the important role of the N-donor in 1A.In addition,as an ionic palladium complex,2A combined with the room-temperature ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate could be recycled eight times as the catalyst in carbonylative Sonogashira reactions without detectable metal leaching.

Multiple objective particle swarm optimization technique for economic load dispatch

A multi-objective particle swarm optimization (MOPSO) approach for multi-objective economic load dispatch problem in power system is presented in this paper. The economic load dispatch problem is a non-linear constrained multi-objective optimization problem. The proposed MOPSO approach handles the problem as a multi-objective problem with competing and non-commensurable fuel cost, emission and system loss objectives and has a diversity-preserving mechanism using an external memory (call “repository”) and a geographically-based approach to find widely different Pareto-optimal solutions. In addition, fuzzy set theory is employed to extract the best compromise solution. Several optimization runs of the proposed MOPSO approach were carried out on the standard IEEE 30-bus test system. The results revealed the capabilities of the proposed MOPSO approach to generate well-distributed Pareto-optimal non-dominated solutions of multi-objective economic load dispatch. Com- parison with Multi-objective Evolutionary Algorithm (MOEA) showed the superiority of the proposed MOPSO approach and confirmed its potential for solving multi-objective economic load dispatch.

Influence of Intermolecular Hydrogen Bonding to Spin Crossover Property of Iron （111） Complexes with a N3O2 Pentadentate Ligand and a Monodentate Ligand

Three iron （III） complexes with the formula of [Feat（X）L2]BPh4 were studied, in which a pentadentate Schiff-base ligand （H2L2 = bis （3-methoxysalicylideneiminopropyl） methylamine） and a counter anion BPh4 were fixed, and three monodentate ligands, 3-Mepy （3-methylpyridine）, 4-NH2py （4-aminopyridine）, and 2-Meim （2-methylimidazole） were used as the axial ligand X. The temperature dependence of magnetic susceptibility measurements demonstrated that [Fem（3-Mepy）L2]BPh4 showed a gradual spin equilibrium between HS （high-spin） （S = 5/2） and LS （low-spin） （S = 1/2） states, [Fem（4-NH2py）L2]BPh4 showed a steep SCO （spin crossover） and [FeIH（2-Melm）L2]BPh4 was in the HS state even at 100 K. The single crystal X-ray analyses demonstrated that [FelH（4-NH2py）L2]BPh4 has an one-dimensional chain structure constructed by intermolecular hydrogen bonding between 4-amino group of 4-NH2py and methoxy oxygen of adjacent molecular-cation. The crystal structure of [FenI（3-Mepy）L2]BPh4 has no such intermolecular interaction and its SCO site behaves independently, and the crystal structure of [FeIII（2-Meim）L2]BPh4 has a NH...n interaction between imidazole group of 2-Meim of cation and a phenyl group of anion BPh4. The result demonstrates that the intermolecular hydrogen bonding affects SCO profile significantly.

Metal complexes of a novel bis-β-diketone-type ligand and its copper(Ⅱ) complexes of two-photon biological imaging

A curcumin derivative ligand,1,7-bis(3-methoxyl-4-acetoxyl)phenyl-1,6-heptadiene-3,5-diketone (diacetylcurcumin,abbreviated as HL),and its Cu and Ni complexes have been synthesized and fully characterized by elemental analyses,IR,1 HNMR and molar conductivity.The resulting complexes exhibit two-photon excited fluorescence (TPEF) in DMF,and have been proven to be potentially useful for two-photon microscopy imaging in living cells.In addition,cytotoxicity tests showed that the low-micromolar concentrations of ML 2 did not cause significant reduction in cell viability over a period of at least 24 h and should be safe for further biological studies.

问题解答

瘧原虫的生活史在蚊体内有配子生殖和胞子生殖的过程,有人说配子生殖为有性生殖,胞子生殖为无性生殖,但又有人不同意这种说去,说配子生殖和胞子生殖均为有性生殖,究竟以何者为对? 瘧原虫在蚊体内的发育肯定是有性生殖而不是无性生殖。这一段生活史通常称为有性生殖循环,但这段生活史严格的说来不是一个循环,因为它只是从雌雄配子配合到形成胞子体为止,而不能从胞子体再在蚊体内转到雌雄配子。