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1.
In this work, the synthesis and characterization of fac-[Re(CO)3(Nqphen)(L)]PF6 complexes is reported. Nqphen is the quinone substituted acceptor ligand [3,2-a:2′,3′-c]-benzo[3,4]-phenazine-11,16-quinone, and L represents the donor monodentate pyridine substituted ligands 4-tert-butylpyridine (t-Bupy), 4-methoxypyridine (MeO-py) or 10-(4-picolyl)phenothiazine (py-PTZ). The complexes were synthesized by refluxing in methanol the metal precursor fac-Re(CO)3(Nqphen)TfO (TfO = trifluoromethanesulphonate anion) with the corresponding L ligand. The UV-Vis spectra of the complexes are dominated by intense intraligand (IL) bands, and less intense metal ligand charge transfer (MLCT) bands with maxima in the 380-400 nm region. The IR shows the typical pattern for tricarbonyl Re complexes with facial (fac) geometry. An additional v(CO) stretching band, attributed to the quinone fragment of Nqphen, is observed.Electrochemical data indicate that the acceptor capacity of Nqphen is increased in the complexes with regard to the free ligand. This effect is sensitive to the nature of the L ligand, following the order: MeO-py < t-Bupy < py-PTZ, indicating therefore that the donor capacity of L affects the rest of the molecule. The results obtained for the fac-[Re (CO)3(Nqphen)(pyPTZ)]PF6 complex here reported were compared with those observed for the homologous complex fac-[Re(CO)3(Aqphen)(L)]0/+, with Aqphen = 12,17-dihydronaphtho[2,3-h]dipyrido[3,2-a:2′,3′-c]-phenazine-12,17-dione, and L = Cl−, TfO−, py-PTZ. 相似文献
2.
Geetika Borah Devajani Boruah Gayatri Sarmah Saitanya K. Bharadwaj Utpal Bora 《应用有机金属化学》2013,27(12):688-694
The reaction of N‐methylimidazole (N‐MeIm) and N‐butylimidazole (N‐BuIm) with the complexes [PdCl2(PPh2py–P,N)] and [PdCl2(PPh2Etpy–P,N)] in the presence of NH4PF6 under N2 at room temperature afforded four new cationic Pd(II) complexes [PdCl(PPh2py–P,N)(N‐MeIm)](PF6) ( 1 ), [PdCl(PPh2py–P,N)(N‐BuIm)](PF6) ( 2 ), [PdCl(PPh2Etpy–P,N)(N‐MeIm)](PF6) ( 4 ) and [PdCl(PPh2Etpy‐P,N)(N‐BuIm)](PF6) ( 5 ) in good yields, where PPh2py is 2‐(diphenylphosphino)pyridine and PPh2Etpy is 2‐{2‐(diphenylphosphino)ethyl}pyridine). The complexes were fully characterized. The catalytic activities of these complexes were investigated for Suzuki–Miyaura cross‐coupling reactions at room temperature. Complex 2 exhibited excellent activity compared to other analogs. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
3.
Cristina Tejel Dr. M. Pilar del Río Dr. Miguel A. Ciriano Prof. Dr. Eduard J. Reijerse Dr. František Hartl Prof. Stanislav Záliš Dr. Dennis G. H. Hetterscheid Dr. Nearchos Tsichlis i Spithas Bas de Bruin Dr. 《Chemistry (Weinheim an der Bergstrasse, Germany)》2009,15(44):11878-11889
Treatment of [Ir(bpa)(cod)]+ complex [ 1 ]+ with a strong base (e.g., tBuO?) led to unexpected double deprotonation to form the anionic [Ir(bpa?2H)(cod)]? species [ 3 ]?, via the mono‐deprotonated neutral amido complex [Ir(bpa?H)(cod)] as an isolable intermediate. A certain degree of aromaticity of the obtained metal–chelate ring may explain the favourable double deprotonation. The rhodium analogue [ 4 ]? was prepared in situ. The new species [M(bpa?2H)(cod)]? (M=Rh, Ir) are best described as two‐electron reduced analogues of the cationic imine complexes [MI(cod)(Py‐CH2‐N?CH‐Py)]+. One‐electron oxidation of [ 3 ]? and [ 4 ]? produced the ligand radical complexes [ 3 ]. and [ 4 ].. Oxygenation of [ 3 ]? with O2 gave the neutral carboxamido complex [Ir(cod)(py‐CH2‐N‐CO‐py)] via the ligand radical complex [ 3 ]. as a detectable intermediate. 相似文献
4.
Chien‐Kuo Hsieh Feng‐Chun Lo Gene‐Hsiang Lee Shie‐Ming Peng Wen‐Feng Liaw 《中国化学会会志》2000,47(1):103-107
Complex fac‐[Fe(CO)3(TePh)3]? was employed as a “metallo chelating” ligand to synthesize the neutral (CO)3Mn(μ‐TePh)3Fe(CO)3 obtained in a one‐step synthesis by treating fac‐[Fe(CO)3(TePh)3]? with fac‐[Mn‐(CO)3(CH3CN)3]+. It seems reasonable to conclude that the d6 Fe(II) [(CO)3Fe(TePh)3]? fragment is isolobal with the d6 Mn(I) [(CO)3Mn(TePh)3]2? fragment in complex (CO)3Mn(μ‐TePh)3Fe(CO)3. Addition of fac‐[Fe(CO)3(TePh)3]? to the CpNi(I)(PPh3) in THF resulted in formation of the neutral CpNi(TePh)(PPh3) also obtained from reaction of CpNi(I)(PPh3) and [Na][TePh] in MeOH. This investigation shows that fac‐[Fe(CO)3(TePh)3]? serves as a tridentate metallo ligand and tellurolate ligand‐transfer reagent. The study also indicated that the fac‐[Fe(CO)3(SePh)3]? may serve as a better tridentate metallo ligand and chalcogenolate ligand‐transfer reagent than fac‐[Fe(CO)3(TePh)3]? in the syntheses of heterometallic chalcogenolate complexes. 相似文献
5.
《Acta Crystallographica. Section C, Structural Chemistry》2018,74(10):1116-1122
The synthesis and characterization of two dinuclear complexes, namely fac‐hexacarbonyl‐1κ3C,2κ3C‐(pyridine‐1κN)[μ‐2,2′‐sulfanediyldi(ethanethiolato)‐1κ2S1,S3:2κ3S1,S2,S3]dirhenium(I), [Re2(C4H8S3)(C5H5N)(CO)6], ( 1 ), and tetraethylammonium fac‐tris(μ‐2‐methoxybenzenethiolato‐κ2S:S)bis[tricarbonylrhenium(I)], (C8H20N)[Re2(C7H7OS)3(CO)6], ( 2 ), together with two mononuclear complexes, namely (2,2′‐bithiophene‐5‐carboxylic acid‐κ2S,S′)bromidotricarbonylrhenium(I), ( 3 ), and bromidotricarbonyl(methyl benzo[b]thiophene‐2‐carboxylate‐κ2O,S)rhenium(I), ( 4 ), are reported. Crystals of ( 1 ) and ( 2 ) were characterized by X‐ray diffraction. The crystal structure of ( 1 ) revealed two Re—S—Re bridges. The thioether S atom only bonds to one of the ReI metal centres, while the geometry of the second ReI metal centre is completed by a pyridine ligand. The structure of ( 2 ) is characterized by three S‐atom bridges and an Re…Re nonbonding distance of 3.4879 (5) Å, which is shorter than the distance found for ( 1 ) [3.7996 (6)/3.7963 (6) Å], but still clearly a nonbonding distance. Complex ( 1 ) is stabilized by six intermolecular hydrogen‐bond interactions and an O…O interaction, while ( 2 ) is stabilized by two intermolecular hydrogen‐bond interactions and two O…π interactions. 相似文献
6.
Christian A. Sandoval Dr. Fusheng Bie Aki Matsuoka Yoshiki Yamaguchi Dr. Hiroshi Naka Prof. Dr. Yuehui Li Koichi Kato Prof. Dr. Noriyuki Utsumi Kunihiko Tsutsumi Takeshi Ohkuma Prof. Dr. Kunihiko Murata Dr. Ryoji Noyori Prof. Dr. 《化学:亚洲杂志》2010,5(4):806-816
Aromatic ketones are enantioseletively hydrogenated in alcohols containing [RuX{(S,S)‐Tsdpen}(η6‐p‐cymene)] (Tsdpen=TsNCH(C6H5)CH(C6H5)NH2; X=TfO, Cl) as precatalysts. The corresponding Ru hydride (X=H) acts as a reducing species. The solution structures and complete spectral assignment of these complexes have been determined using 2D NMR (1H‐1H DQF‐COSY, 1H‐13C HMQC, 1H‐15N HSQC, and 1H‐19F HOESY). Depending on the nature of the solvents and conditions, the precatalysts exist as a covalently bound complex, tight ion pair of [Ru+(Tsdpen)(cymene)] and X?, solvent‐separated ion pair, or discrete free ions. Solvent effects on the NH2 chemical shifts of the Ru complexes and the hydrodynamic radius and volume of the Ru+ and TfO? ions elucidate the process of precatalyst activation for hydrogenation. Most notably, the Ru triflate possessing a high ionizability, substantiated by cyclic voltammetry, exists in alcoholic solvents largely as a solvent‐separated ion pair and/or free ions. Accordingly, its diffusion‐derived data in CD3OD reflect the independent motion of [Ru+(Tsdpen)(cymene)] and TfO?. In CDCl3, the complex largely retains the covalent structure showing similar diffusion data for the cation and anion. The Ru triflate and chloride show similar but distinct solution behavior in various solvents. Conductivity measurements and catalytic behavior demonstrate that both complexes ionize in CH3OH to generate a common [Ru+(Tsdpen)(cymene)] and X?, although the extent is significantly greater for X=TfO?. The activation of [RuX(Tsdpen)(cymene)] during catalytic hydrogenation in alcoholic solvent occurs by simple ionization to generate [Ru+(Tsdpen)(cymene)]. The catalytic activity is thus significantly influenced by the reaction conditions. 相似文献
7.
Dr. Ramachandran Azhakar Dr. Rajendra S. Ghadwal Prof. Dr. Herbert W. Roesky Jakob Hey Prof. Dr. Dietmar Stalke 《化学:亚洲杂志》2012,7(3):528-533
Three transition‐metal–carbonyl complexes [V( L )(CO)3(Cp)] ( 1 ), [Co( L )(CO)(Cp)] ( 2 ), and [Co( L2 )(CO)3]+[CoCO)4]? ( 3 ), each containing stable N‐heterocyclic‐chlorosilylene ligands ( L ; L =PhC(NtBu)2SiCl) were synthesized from [V(CO)4(Cp)], [Co(CO)2(Cp)], and Co2(CO)8, respectively. Complexes 1 , 2 , 3 were characterized by NMR and IR spectroscopy, EI‐MS spectrometry, and elemental analysis. The molecular structures of compounds 1 , 2 , 3 were determined by single‐crystal X‐ray diffraction. 相似文献
8.
Kuang‐Hway Yih 《中国化学会会志》2003,50(5):1109-1113
The conformational isomers endo‐ and exo‐[Mo{η3‐C3H4(CH3)}(η2‐pyS)(CO)(η2‐diphos)] (diphos: dppm = {bis(diphenylphosphino)methane}, 2 ; dppe = {1,2‐bis(diphenylphosphino)ethane}, 3 ) are prepared by reacting the double‐bridged pyridine‐2‐thionate (pyS) complex [Mo{η3‐C3H4(CH3)}(CO)2]2(η1:η2:μ‐pyS)2, 1 with diphos in refluxing acetonitrile. Stereoselectivity of the methallyl, C3H4(CH3), ligand improves the formation of the exo‐conformation of 2 and 3 . Orientations and spectroscopy of these complexes are discussed. 相似文献
9.
《Acta Crystallographica. Section C, Structural Chemistry》2017,73(11):923-929
Carbon monoxide (CO) has recently been identified as a gaseous signaling molecule that exerts various salutary effects in mammalian pathophysiology. Photoactive metal carbonyl complexes (photoCORMs) are ideal exogenous candidates for more controllable and site‐specific CO delivery compared to gaseous CO. Along this line, our group has been engaged for the past few years in developing group‐7‐based photoCORMs towards the efficient eradication of various malignant cells. Moreover, several such complexes can be tracked within cancerous cells by virtue of their luminescence. The inherent luminecscent nature of some photoCORMs and the change in emission wavelength upon CO release also provide a covenient means to track the entry of the prodrug and, in some cases, both the entry and CO release from the prodrug. In continuation of the research circumscribing the development of trackable photoCORMs and also to graft such molecules covalently to conventional delivery vehicles, we report herein the synthesis and structures of three rhenium carbonyl complexes, namely, fac‐tricarbonyl[2‐(pyridin‐2‐yl)‐1,3‐benzothiazole‐κ2N ,N ′](4‐vinylpyridine‐κN )rhenium(I) trifluoromethanesulfonate, [Re(C7H7N)(C12H8N2S)(CO)3](CF3SO3), ( 1 ), fac‐tricarbonyl[2‐(quinolin‐2‐yl)‐1,3‐benzothiazole‐κ2N ,N ′](4‐vinylpyridine‐κN )rhenium(I) trifluoromethanesulfonate, [Re(C7H7N)(C16H10N2S)(CO)3](CF3SO3), ( 2 ), and fac‐tricarbonyl[1,10‐phenanthroline‐κ2N ,N ′](4‐vinylpyridine‐κN )rhenium(I) trifluoromethanesulfonate, [Re(C7H7N)(C12H8N2)(CO)3](CF3SO3), ( 3 ). In all three complexes, the ReI center resides in a distorted octahedral coordination environment. These complexes exhibit CO release upon exposure to low‐power UV light. The apparent CO release rates of the complexes have been measured to assess their comparative CO‐donating capacity. The three complexes are highly luminescent and this in turn provides a convenient way to track the entry of the prodrug molecules within biological targets. 相似文献
10.
Dorothy H. Gibson Mark S. Mashuta Xiaolong Yin 《Acta Crystallographica. Section C, Structural Chemistry》2004,60(8):m366-m367
The title organometallic compound, fac‐tricarbonyl‐2κ3C‐(4,4′‐dimethyl‐2,2′‐bipyridine)‐2κ2N,N′‐triphenyl‐1κ3C1‐tin(II)rhenium(I)(Sn—Re), [ReSn(C6H5)3(C12H12N2)(CO)3], contains three unique π–π stacking interactions. The result is an infinite chain of uninterrupted alternating intra‐ and intermolecular offset π–π stacking interactions throughout the crystal lattice. This extended π–π stacking arrangement, and an additional isolated intramolecular π–π interaction between the remaining 4,4′‐dimethyl‐2,2′‐bipyridine ring and a second phenyl group, impose geometric constraints on the Re and Sn atoms, yielding distorted octahedral and tetrahedral coordinations, respectively, for the metal centers. 相似文献
11.
Zhuming Guo Jing Jin Zhiyin Xiao Naiwen Chen Xiujuan Jiang Xiaoming Liu Lingfeng Wu Yi He Shuhua Zhang 《应用有机金属化学》2021,35(1)
Four iron(II) carbonyl complexes, fac‐[Fe (CO)3X2(py)] (X = I?, 1 and Br?, 3 ), fac‐[{Fe (CO)3X2}2(bipy)] (X = I?, 2 and Br?, 4 ), were facilely synthesized by reacting cis‐[Fe (CO)4X2] (X = I?, Br?) with pyridine (py) and 4,4′‐dipyridine (bipy) ligands, respectively, in good yields (70%~85%). These complexes were fully characterized, and the structures of Complexes 2 and 3 were crystallographically analyzed. In dimethyl sulfoxide, they decomposed rapidly to release carbon monoxide (CO), and in methanol, they showed better stability which allowed kinetically analyzing their decomposing behaviors. The self‐decomposing in methanol fitted first‐order kinetics with a half‐time ranging from several minutes to 1 h. Our results suggested that the ligand with great conjugation (bipy) and strong electron‐donating capability (iodide) could stabilize the iron(II) carbonyl complexes. The decomposition of the iodo complexes ( 1 and 2 ) involved the production of iodine radicals. MTT (3‐(4,5‐dimethylthiazol‐2‐yl)‐2,5‐diphenyl tetrazolium bromide) assessments revealed that the efficacy against human bladder carcinoma cell line (RT112) is in the following trend: 1 > 2 > 3 > 4 . The relatively strong efficacy of Complexes 1 and 2 is mainly contributed to the in situ generated iodine radicals. The combination of the cytotoxicity of the in situ generated radicals with the anticancer activity of CO as reported in literatures may lead to developing novel anticancer drugs with enhanced efficacy. 相似文献
12.
Cristiano Zuccaccia Gianfranco Bellachioma Giuseppe Cardaci Alceo Macchioni Barbara Binotti Carla Carfagna 《Helvetica chimica acta》2006,89(8):1524-1546
Palladacyclic compounds [Pd(C6H4(C6H5C?O)C?N? R)(N? N)] [X] (R = Et, iPr, 2,6‐iPr2C6H3; N? N = bpy = 2,2′‐bipyridine, or 1,4‐(o,o′‐dialkylaryl)‐1,4‐diazabuta‐1,3‐dienes; [X]? = [BF4]? or [PF6]?) were synthesized from the dimers [{Pd(C6H4(C6H5C?O)C?N? R)(μ‐Cl)}2] and N? N ligands. Their interionic structure in CD2Cl2 was determined by means of 19F,1H‐HOESY experiments and compared with that in the solid state derived from X‐ray single‐crystal studies. [Pd(C6H4(C6H5C?O)C?N? R)(N? N)] [X] complexes were found to copolymerize CO and p‐methylstyrene affording syndiotactic or isotactic copolymers when bpy or 1,4‐(o,o′‐dimethylaryl)‐1,4‐diazabuta‐1,3‐dienes were used, respectively. The reactions with CO and p‐methylstyrene of the bpy derivatives were investigated. Two intermediates derived from a single and a double insertion of CO into the Pd? C bonds were isolated and completely characterized in solution. 相似文献
13.
Alcohol oxidation reactions catalyzed by ruthenium–carbonyl complexes of thioarylazoimidazoles
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Shyamal Kumar Sarkar Mahendra Sekhar Jana Tapan Kumar Mondal Chittaranjan Sinha 《应用有机金属化学》2014,28(8):641-651
Alcohols are oxidized by N‐methylmorpholine‐N‐oxide (NMO), ButOOH and H2O2 to the corresponding aldehydes or ketones in the presence of catalyst, [RuH(CO)(PPh3)2(SRaaiNR′)]PF6 ( 2 ) and [RuCl(CO)(PPh3)(SκRaaiNR′)]PF6 ( 3 ) (SRaaiNR′ ( 1 ) = 1‐alkyl‐2‐{(o‐thioalkyl)phenylazo}imidazole, a bidentate N(imidazolyl) (N), N(azo) (N′) chelator and SκRaaiNR′ is a tridentate N(imidazolyl) (N), N(azo) (N′), Sκ‐R is tridentate chelator; R and R′ are Me and Et). The single‐crystal X‐ray structures of [RuH(CO)(PPh3)2(SMeaaiNMe)]PF6 ( 2a ) (SMeaaiNMe = 1‐methyl‐2‐{(o‐thioethyl)phenylazo}imidazole) and [RuH(CO)(PPh3)2(SEtaaiNEt)]PF6 ( 2b ) (SEtaaiNEt = 1‐ethyl‐2‐{(o‐thioethyl)phenylazo}imidazole) show bidentate N,N′ chelation, while in [RuCl(CO)(PPh3)(SκEtaaiNEt)]PF6 ( 3b ) the ligand SκEtaaiNEt serves as tridentate N,N′,S chelator. The cyclic voltammogram shows RuIII/RuII (~1.1 V) and RuIV/RuIII (~1.7 V) couples of the complexes 2 while RuIII/RuII (1.26 V) couple is observed only in 3 along with azo reductions in the potential window +2.0 to ?2.0 V. DFT computation has been used to explain the spectra and redox properties of the complexes. In the oxidation reaction NMO acts as best oxidant and [RuCl(CO)(PPh3)(SκRaaiNR′)](PF6) ( 3 ) is the best catalyst. The formation of high‐valent RuIV=O species as a catalytic intermediate is proposed for the oxidation process. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
14.
Rhenium Dicarbonyl‐Nitrosyl Complexes with Imidazole Different rhenium‐dicarbonyl‐nitrosyl complexes with imidazole (Im) as monodentate ligand have been synthesized and characterized, starting from [NEt4][ReCl3(CO)2(NO)] and [ReCl(μ?Cl)(CO)2(NO)]2. Whereas the complexes [ReCl2(Im)(CO)2(NO)] and [ReCl(Im)2(CO)2(NO)]+ were achieved in high yields, the complex [Re(Im)3(CO)2(NO)]2+ with three imidazole ligands could only be isolated after complete removal of all halide ions (with AgBF4) in low yield. The synthesis of a corresponding 99mTc‐dicarbonyl‐nitrosyl complex with imidazole opens a new perspective for such compounds as potential radiopharmaceuticals and alternatives to the already established 99mTc‐tricarbonyl complexes. 相似文献
15.
Syntheses,Structures, and Electrochemical Properties of Two Bis‐triazole‐bis‐amide‐based Copper(II) Pyridine‐2,3‐dicarboxylate Coordination Polymers
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Abstract. Two bis‐triazole‐bis‐amide‐based copper(II) pyridine‐2,3‐dicarboxylate coordination polymers (CPs), [Cu(2,3‐pydc)(dtb)0.5(DMF)] · 2H2O ( 1 ) and [Cu(2,3‐pydc)(dth)0.5(DMF)] · 2H2O ( 2 ) (2,3‐H2pydc = pyridine‐2,3‐dicarboxylic acid, dtb = N,N′‐bis(4H‐1,2,4‐triazole)butanamide, and dth = N,N′‐bis(4H‐1,2,4‐triazole)hexanamide), were synthesized under solvothermal conditions. CPs 1 and 2 show similar two‐dimensional (2D) structures. In 1 , the 2,3‐pydc anions bridge the CuII ions into a one‐dimensional (1D) chain. Such 1D chains are linked by the dtb ligands to form a 2D layer. The adjacent 2D layers are extended into a three‐dimensional (3D) supramolecular architecture by hydrogen‐bonding interactions. The electrochemical properties of 1 and 2 were investigated. 相似文献
16.
《Journal of organometallic chemistry》1986,302(1):47-58
The complexes fac-[XMn(CO)3(dppm)], cis,cis-[XMn(CO)2(dppm)(P(OPh)3)] and trans-[XMn(CO)(dppm)2] with X = SCN or CN have been prepared from the corresponding bromocarbonyls and the salts AgX or KX, or, in the case of the di- and mono-carbonyls, from fac-[XMn(CO)3(dppm)] with X = SCN or CN by thermal or photochemical CO substitution by the ligands P(OPh)3 or dppm. The structure of fac-[SCNMn(CO)3(dppm)] has been determined by X-ray diffraction. The crystals are monoclinic, space group P21/n, and the structure has been refined to R = 0.058 for 4123 reflexions measured in the range 2 ⩽ θ ⩽ 30 at room temperature. The cis,cis-[NCMn(CO)2(dppm)(P(OPh)3)] complex can be oxidized and subsequently reduced to the isomer trans-[NCMn(CO)2(dppm)(P(OPh)3)]. All the neutral cyanide complexes react readily with MeI and KPF6 to give the corresponding methylisocyanide derivatives [Mn(CO)2(dppm)(P(OPh)3)(CNMe)]PF6 and [Mn(CO)(dppm)2(CNMe)]PF6. The stereochemistries of the compounds is discussed in relation to the 31P NMR spectra. 相似文献
17.
Self‐Assembly of Five 8‐Hydroxyquinolinate‐Based Complexes: Tunable Core,Supramolecular Structure,and Photoluminescence Properties
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Prof. Dr. Guozan Yuan Weilong Shan Xuelong Qiao Li Ma Prof. Dr. Yanping Huo 《化学:亚洲杂志》2014,9(7):1913-1921
Five new ZnII complexes, namely [Zn3(L)6] ( 1 ), [Zn2(Cl)2(L)2(py)2] ( 2 ), [Zn2(Br)2(L)2(py)2] ( 3 ), [Zn(L)2(py)] ( 4 ), and [Zn2(OAc)2(L)2(py)2] ( 5 ), were prepared by the solvothermal reaction of ZnX2 (X?=Cl?, Br?, F?, and OAc?) salts with a 8‐hydroxyquinolinate ligand (HL) that contained a trifluorophenyl group. All of the complexes were characterized by elemental analysis, IR spectroscopy, and powder and single‐crystal X‐ray crystallography. The building blocks exhibited unprecedented structural diversification and their self‐assembly afforded one mononuclear, three binuclear, and one trinuclear ZnII structures in response to different anions and solvent systems. Complexes 1 – 5 featured four types of supramolecular network controlled by non‐covalent interactions, such as π???π‐stacking, C? H???π, hydrogen‐bonding, and halogen‐related interactions. Investigation of their photoluminescence properties exhibited disparate emission wavelengths, lifetimes, and quantum yields in the solid state. 相似文献
18.
Munechika Nakamura Yoshimi Tsukamoto Takuro Ueta Yoshihisa Sei Takanori Fukushima Kenji Yoza Kenji Kobayashi 《化学:亚洲杂志》2020,15(14):2218-2230
A 2 : 4 mixture of tetrakis[4‐(4‐pyridyl)phenyl]cavitand ( 1 ) or tetrakis[4‐(4‐pyridyl)phenylethynyl]cavitand ( 2 ) and Pd(dppp)(OTf)2 self‐assembles into a homocapsule { 1 2 ? [Pd(dppp)]4}8+ ? (TfO?)8 ( C1 ) or { 2 2 ? [Pd(dppp)]4}8+ ? (TfO?)8 ( C2 ), respectively, through Pd?Npy coordination bonds. A 1 : 1 : 4 mixture of 1 , 2 , and Pd(dppp)(OTf)2 produced a mixture of homocapsules C1 , C2 , and a heterocapsule { 1 ? 2 ? [Pd(dppp)]4}8+ ? (TfO?)8 ( C3 ) in a 1 : 1 : 0.98 mole ratio. Selective formation (self‐sorting) of homocapsules C1 and C2 or heterocapsule C3 was controlled by guest‐induced encapsulation under thermodynamic control. Applications of Pd?Npy coordination capsules with the use of 1 were demonstrated. Capsule C1 serves as a guard nanocontainer for trans‐4,4′‐diacetoxyazobenzene to protect against the trans‐to‐cis photoisomerization by encapsulation. A chiral capsule { 1 2 ? [Pd((R)‐BINAP)]4}8+ ? (TfO?)8 ( C5 ) was also constructed. Capsule C5 induces supramolecular chirality with respect to prochiral 2,2′‐bis(alkoxycarbonyl)‐4,4′‐bis(1‐propynyl)biphenyls by diastereomeric encapsulation through the asymmetric suppression of rotation around the axis of the prochiral biphenyl moiety. 相似文献
19.
GustavoT. Ruiz MariaP. Juliarena ReynaldoO. Lezna Ezequiel Wolcan MarioR. Feliz Guillermo Ferraudi 《Helvetica chimica acta》2002,85(5):1261-1275
The photophysical and photochemical properties of (OC‐6‐33)‐(2,2′‐bipyridine‐κN1,κN1′)tricarbonyl(9,10‐dihydro‐9,10‐dioxoanthracene‐2‐carboxylato‐κO)rhenium (fac‐[ReI(aq‐2‐CO2)(2,2′‐bipy)(CO)3]) were investigated and compared to those of the free ligand 9,10‐dihydro‐9,10‐dioxoanthracene‐2‐carboxylate (=anthraquinone‐2‐carboxylate) and other carboxylato complexes containing the (2,2′‐bipyridine)tricarbonylrhenium ([Re(2,2′‐bipy)(CO)3]) moiety. Flash and steady‐state irradiations of the anthraquinone‐derived ligand (λexc 337 or 351 nm) and of its complex reveal that the photophysics of the latter is dominated by processes initiated in the Re‐to‐(2,2′‐bipyridine) charge‐transfer excited state and 2,2′‐bipyridine‐ and (anthraquinone‐2‐carboxylato)‐centered intraligand excited states. In the reductive quenching by N,N‐diethylethanamine (TEA) or 2,2′,2″‐nitrilotris[ethanol] TEOA, the reactive states are the 2,2′‐bipyridine‐centered and/or the charge‐transfer excited states. The species with a reduced anthraquinone moiety is formed by the following intramolecular electron transfer, after the redox quenching of the excited state: [ReI(aq−2−CO2)(2,2′‐bipy.)(CO)3]−⇌[ReI(aq−2−CO2.)(2,2′‐bipy)(CO)3]− The photophysics, particularly the absence of a ReI‐to‐anthraquinone charge‐transfer excited state photochemistry, is discussed in terms of the electrochemical and photochemical results. 相似文献
20.
Marcin Konkol Christoph Wagner Sebastian Schwieger Ronald Lindner Dirk Steinborn 《无机化学与普通化学杂志》2005,631(8):1456-1462
[K(18C6)]2[Pd2Cl6] ( 1 ) (18C6 = 18‐crown‐6) was found to react with pyridines in a strictly stoichiometric ratio 1 : 2 in methylene chloride or nitromethane to yield trichloropalladate(II) complexes [K(18C6)][PdCl3(py*)] (py* = py, 2a ; 4‐Bnpy, 2b ; 4‐tBupy, 2c ; Bn = benzyl; tBu = tert‐butyl). The reaction of 1 with pyrimidine (pyrm) in a 1 : 1 ratio led to the formation of the pyrimidine‐bridged bis(trichloropalladate) complex [K(18C6)]2[(PdCl3)2(μ‐pyrm)] ( 3 ). The identities of the complexes were confirmed by means of NMR spectroscopy (1H, 13C) and microanalysis. The X‐ray structure analysis of 2a reveals square‐planar coordination of the Pd atom in the [PdCl3(py)]? anion. The pyridine plane forms with the complex plane an angle of 55.8(2)°. In the [K(18C6)]+ cation the K+ lies outside the mean plane of the crown ether (defined by the 6 O atoms) by 0.816(1) Å. There are tight K···Cl contacts between the cation and the anion (K···Cl1 3.340(2) Å, K···Cl2 3.166(2) Å). To gain an insight into the conformation of the [PdCl3(py)]? anion, DFT calculations were performed showing that the equilibrium structure ( 6eq ) has an angle between the pyridine ligand and the complex plane of 35.3°. Rotation of the pyridine ligand around the Pd–N vector exhibited two transition states where the pyridine ligand lies either in the complex plane ( 6TS pla, 0.87 kcal/mol above 6eq ) or is perpendicular to it ( 6TS per, 3.76 kcal/mol above 6eq ). Based on an energy decomposition analysis the conformation of the anion is discussed in terms of repulsive steric interactions and of stabilizing σ and π orbital interactions between the PdCl3? moiety and the pyridine ligand. 相似文献