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351.
Hui‐Xian Yeong Dr. Hong‐Wei Xi Dr. Yongxin Li Prof. Dr. Kok Hwa Lim Dr. Cheuk‐Wai So 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(35):11786-11790
The synthesis and reactivity of a silyliumylidene cation stabilized by an amidinate ligand and 4‐dimethylaminopyridine (DMAP) are described. The reaction of the amidinate silicon(I) dimer [ L Si:]2 ( 1 ; L =PhC(NtBu)2) with one equivalent of N‐trimethylsilyl‐4‐dimethylaminopyridinium triflate [4‐NMe2C5H4NSiMe3]OTf and two equivalents of DMAP in THF afforded [ L Si(DMAP)]OTf ( 2 ). The ambiphilic character of 2 is demonstrated from its reactivity. Treatment of 2 with 1 in THF afforded the disilylenylsilylium triflate [ L′ 2( L )Si]OTf ( 3 ; L′ = L Si:) with the displacement of DMAP. The reaction of 2 with [K{HB(iBu)3}] and elemental sulfur in THF afforded the silylsilylene [ L SiSi(H){(NtBu)2C(H)Ph}] ( 4 ) and the base‐stabilized silanethionium triflate [ L Si(S)DMAP]OTf ( 5 ), respectively. Compounds 2 , 3 , and 5 have been characterized by X‐ray crystallography. 相似文献
352.
Benjamin M. Gridley Dr. Graeme J. Moxey Dr. William Lewis Prof. Alexander J. Blake Dr. Deborah L. Kays 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(34):11446-11453
The synthesis and characterization of the first series of low‐coordinate bis(terphenyl) complexes of the Group 12 metals, [Zn(2,6‐Naph2C6H3)2] ( 1 ), [Cd(OEt2)(2,6‐Naph2C6H3)2] ( 2 ) and [Hg(OEt2)(2,6‐Naph2C6H3)2] ( 3 ) (Naph=1‐C10H7) are described. The naphthyl substituents of the terphenyl ligands confer considerable steric bulk, and as a result of limited flexibility introduce multiple conformations to these unusual systems. In the solid state, complex 1 features a two‐coordinate Zn centre with the ligands oriented in a syn/anti conformation, whereas the three‐coordinate distorted T‐shaped complexes 2 and 3 feature the ligands in the syn/syn configurations. The results of DFT calculations are in good agreement with the solid‐state configurations for these complexes and support the spectroscopic measurements, which indicate several conformers in solution. 相似文献
353.
Aaron Breivogel Michael Meister Dr. Christoph Förster Dr. Frédéric Laquai Prof. Dr. Katja Heinze 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(41):13745-13760
The synergy of push–pull substitution and enlarged ligand bite angles has been used in functionalized heteroleptic bis(tridentate) polypyridine complexes of ruthenium(II) to shift the 1MLCT absorption and the 3MLCT emission to lower energy, enhance the emission quantum yield, and to prolong the 3MLCT excited‐state lifetime. In these complexes, that is, [Ru(ddpd)(EtOOC‐tpy)][PF6]2, [Ru(ddpd‐NH2)(EtOOC‐tpy)][PF6]2, [Ru(ddpd){(MeOOC)3‐tpy}][PF6]2, and [Ru(ddpd‐NH2){(EtOOC)3‐tpy}][PF6]2 the combination of the electron‐accepting 2,2′;6′,2′′‐terpyridine (tpy) ligand equipped with one or three COOR substituents with the electron‐donating N,N′‐dimethyl‐N,N′‐dipyridin‐2‐ylpyridine‐2,6‐diamine (ddpd) ligand decorated with none or one NH2 group enforces spatially separated and orthogonal frontier orbitals with a small HOMO–LUMO gap resulting in low‐energy 1MLCT and 3MLCT states. The extended bite angle of the ddpd ligand increases the ligand field splitting and pushes the deactivating 3MC state to higher energy. The properties of the new isomerically pure mixed ligand complexes have been studied by using electrochemistry, UV/Vis absorption spectroscopy, static and time‐resolved luminescence spectroscopy, and transient absorption spectroscopy. The experimental data were rationalized by using density functional calculations on differently charged species (charge n=0–4) and on triplet excited states (3MLCT and 3MC) as well as by time‐dependent density functional calculations (excited singlet states). 相似文献
354.
Feng Huang Ying‐Ying Pei Hui‐Hui Zuo Jia‐Liang Chen Yin Yang Prof. Xun‐Cheng Su 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(50):17141-17149
Site‐specific labeling of proteins with lanthanide ions offers great opportunities for investigating the structure, function, and dynamics of proteins by virtue of the unique properties of lanthanides. Lanthanide‐tagged proteins can be studied by NMR, X‐ray, fluorescence, and EPR spectroscopy. However, the rigidity of a lanthanide tag in labeling of proteins plays a key role in the determination of protein structures and interactions. Pseudocontact shift (PCS) and paramagnetic relaxation enhancement (PRE) are valuable long‐range structure restraints in structural‐biology NMR spectroscopy. Generation of these paramagnetic restraints generally relies on site‐specific tagging of the target proteins with paramagnetic species. To avoid nonspecific interaction between the target protein and paramagnetic tag and achieve reliable paramagnetic effects, the rigidity, stability, and size of lanthanide tag is highly important in paramagnetic labeling of proteins. Here 4′‐mercapto‐2,2′: 6′,2′′‐terpyridine‐6,6′′‐dicarboxylic acid (4MTDA) is introduced as a a rigid paramagnetic and fluorescent tag which can be site‐specifically attached to a protein by formation of a disulfide bond. 4MTDA can be readily immobilized by coordination of the protein side chain to the lanthanide ion. Large PCSs and RDCs were observed for 4MTDA‐tagged proteins in complexes with paramagnetic lanthanide ions. At an excitation wavelength of 340 nm, the complex formed by protein–4MTDA and Tb3+ produces high fluorescence with the main emission at 545 nm. These interesting features of 4MTDA make it a very promising tag that can be exploited in NMR, fluorescence, and EPR spectroscopic studies on protein structure, interaction, and dynamics. 相似文献
355.
356.
357.
Dr. Dipanwita Das Hemlata Agarwala Dr. Abhishek Dutta Chowdhury Tuhin Patra Dr. Shaikh M. Mobin Prof. Dr. Biprajit Sarkar Prof. Dr. Wolfgang Kaim Prof. Dr. Goutam Kumar Lahiri 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(23):7384-7394
The complex series [Ru(pap)(Q)2]n ([ 1 ]n–[ 4 ]n; n=+2, +1, 0, ?1, ?2) contains four redox non‐innocent entities: one ruthenium ion, 2‐phenylazopyridine (pap), and two o‐iminoquinone moieties, Q=3,5‐di‐tert‐butyl‐N‐aryl‐1,2‐benzoquinonemonoimine (aryl=C6H5 ( 1+ ); m‐(Cl)2C6H3 ( 2+ ); m‐(OCH3)2C6H3 ( 3+ ); m‐(tBu)2C6H3 ( 4 +)). A crystal structure determination of the representative compound, [ 1 ]ClO4, established the crystallization of the ctt‐isomeric form, that is, cis and trans with respect to the mutual orientations of O and N donors of two Q ligands, and the coordinating azo N atom trans to the O donor of Q. The sensitive C? O (average: 1.299(3) Å), C? N (average: 1.346(4) Å) and intra‐ring C? C (meta; average: 1.373(4) Å) bond lengths of the coordinated iminoquinone moieties in corroboration with the N?N length (1.292(3) Å) of pap in 1 + establish [RuIII(pap0)(Q.?)2]+ as the most appropriate electronic structural form. The coupling of three spins from one low‐spin ruthenium(III) (t2g5) and two Q.? radicals in 1 +– 4 + gives a ground state with one unpaired electron on Q.?, as evident from g=1.995 radical‐type EPR signals for 1 +– 4 +. Accordingly, the DFT‐calculated Mulliken spin densities of 1 + (1.152 for two Q, Ru: ?0.179, pap: 0.031) confirm Q‐based spin. Complex ions 1 +– 4 + exhibit two near‐IR absorption bands at about λ=2000 and 920 nm in addition to intense multiple transitions covering the visible to UV regions; compounds [ 1 ]ClO4–[ 4 ]ClO4 undergo one oxidation and three separate reduction processes within ±2.0 V versus SCE. The crystal structure of the neutral (one‐electron reduced) state ( 2 ) was determined to show metal‐based reduction and an EPR signal at g=1.996. The electronic transitions of the complexes 1 n– 4 n (n=+2, +1, 0, ?1, ?2) in the UV, visible, and NIR regions, as determined by using spectroelectrochemistry, have been analyzed by TD‐DFT calculations and reveal significant low‐energy absorbance (λmax>1000 nm) for cations, anions, and neutral forms. The experimental studies in combination with DFT calculations suggest the dominant valence configurations of 1 n– 4 n in the accessible redox states to be [RuIII(pap0)(Q.?)(Q0)]2+ ( 1 2+– 4 2+)→[RuIII(pap0)(Q.?)2]+ ( 1 +– 4 +)→[RuII(pap0)(Q.?)2] ( 1 – 4 )→[RuII(pap.?)(Q.?)2]? ( 1 ?– 4 ?)→[RuIII(pap.?)(Q2?)2]2? ( 1 2?– 4 2?). 相似文献
358.
Prof. Dr. Mutsumi Kimura Junya Masuo Yuki Tohata Kazumichi Obuchi Naruhiko Masaki Takurou N. Murakami Nagatoshi Koumura Kojiro Hara Atsushi Fukui Ryohsuke Yamanaka Prof. Dr. Shogo Mori 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):1028-1034
A series of panchromatic ruthenium sensitizers ( MJ sensitizers) with attached thiophene and phenyl units bearing alkyl chains was synthesized. A new synthetic route was used to examine all possible positions for the alkyl chains. The absorption spectra showed the sum of a ruthenium complex and peripheral organic chromophore units. The hypochromic effect and blueshift of the metal‐to‐ligand charge‐transfer band observed in the modified ruthenium sensitizers were suppressed by changing the positions of the alkyl chains on the attached thiophene ring. Changing only one alkyl chain also influenced the performance of dye‐sensitized solar cells. Ruthenium sensitizer MJ‐10 with bulky substituent harvests visible and near‐infrared light, and solar cells sensitized by MJ‐10 exhibit an efficiency of 9.1 % under 1 sun irradiation. 相似文献
359.
Dr. Yun Wang Dr. Jin Yang Dr. Ying‐Ying Liu Prof. Dr. Jian‐Fang Ma 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(43):14591-14599
Two porous metal–organic frameworks (MOFs), [Zn3(L)(H2O)2] ? 3 DMF ? 7 H2O ( MOF‐1 ) and [(CH3)2NH2]6[Ni3(L)2(H2O)6] ? 3 DMF ? 15 H2O ( MOF‐2 ), were synthesized solvothermally (H6L=1,2,3,4,5,6‐hexakis(3‐carboxyphenyloxymethylene)benzene). In MOF ‐ 1 , neighboring ZnII trimers are linked by the backbones of L ligands to form a fascinating 3D six‐connected framework with the point symbol (412.63) (412.63). In MOF‐2 , eight L ligands bridge six NiII atoms to generate a rhombic‐dodecahedral [Ni6L8] cage. Each cage is surrounded by eight adjacent ones through sharing of carboxylate groups to yield an unusual 3D porous framework. Encapsulation of LnIII cations for tunable luminescence and small drug molecules for efficient delivery were investigated in detail for MOF‐1 . 相似文献
360.
Two new silver(I) trans‐cinnamates, namely [Ag(2‐cca)(H2O)]2 ( 1 ) and [Ag(4‐cca)]n ( 2 ) (2‐ccaH = 2‐chlorocinnamic acid and 4‐ccaH = 4‐chlorocinnamic acid), were synthesized and structurally characterized. Single crystal X‐ray studies reveal that each silver(I) atom in 1 is two‐coordinate by a 2‐chlorocinnamate ligand and one water molecule to afford a discrete centrosymmetric dimer with the ligand‐unsupported Ag···Ag interactions (3.218(4) Å), while a pair of symmetry‐related silver(I) atoms in 2 are clamped by two μ2‐η1:η1 4‐chlorocinnamate ligands to yield a binuclear silver(I) moiety incorporating a ligand‐supported Ag···Ag interaction (2.819(5) Å). Both complexes 1 and 2 show potent urease inhibitory activities with the respective IC50 values of 0.66 and 1.10 μM. 相似文献