共查询到20条相似文献,搜索用时 15 毫秒
1.
A New Structural Motif for an Enantiomerically Pure Metallosupramolecular Pd4L8 Aggregate by Anion Templating
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
M. Sc. Christoph Klein Dr. Christoph Gütz Maximilian Bogner M. Sc. Filip Topić Prof. Dr. Kari Rissanen Prof. Dr. Arne Lützen 《Angewandte Chemie (International ed. in English)》2014,53(14):3739-3742
An enantiomerically pure BINOL‐based bis(3‐pyridyl) ligand 1 assembles into a homochiral [Pd4( 1 )8] complex upon coordination to tetravalent PdII ions. The formation of this aggregate is templated by two tetrafluoroborate counterions that are encapsulated in two peripheral cavities. The resulting structure is a new structural motif for this kind of metallosupramolecular assemblies that arranges the palladium ions in a distorted tetrahedral fashion and forces ligand 1 to adopt two different conformations. Both phenomena are unique and cause an overall three‐dimensional structure that has another confined, chiral, and hydrophilic central cavity. 相似文献
2.
3.
Dipl.‐Chem. Rainer Hovorka Dipl.‐Chem. Georg Meyer‐Eppler Dipl.‐Chem. Torsten Piehler Sophie Hytteballe Dr. Marianne Engeser Filip Topić Prof. Dr. Kari Rissanen Prof. Dr. Arne Lützen 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(41):13253-13258
Two enantiomerically pure 9,9′‐spirobifluorene‐based bis(pyridine) ligands 1 and 2 were prepared to study their self‐assembly behavior upon coordination to cis‐protected palladium(II) ions. Whereas the sterically more demanding ligand, 2 , gave rise to the expected dinuclear metallosupramolecular M2L2 rhombi, the sterically less demanding ligand, 1 , acts as a template to give rise to a homochiral metallosupramolecular M4L4 catenane. 相似文献
4.
Roan A. S. Vasdev Dr. James A. Findlay Dr. David R. Turner Prof. James D. Crowley 《化学:亚洲杂志》2021,16(1):39-43
A new ferrocene-containing [Pd3( L4EFc )6]6+(X−)6 ( C ⋅ BF4 and C ⋅ SbF6 where X=BF4− or SbF6−) self-assembled double-walled triangle has been synthesized from the known, rotationally flexible, 1,1′-bis(4-pyridylethynyl)ferrocene ligand ( L4EFc ), and characterized by 1H, 13C and diffusion ordered (DOSY) NMR spectroscopies, high-resolution electrospray ionization mass spectrometry (HR−ESI−MS), X-ray crystallography and cyclic voltammetry (CV). The molecular structures confirmed that double-walled triangle cage systems ( C ⋅ BF4 and C ⋅ SbF6 ) were generated. C ⋅ BF4 was shown to interact with the anionic guest, p-toluenesulfonate. CV experiments revealed that the triangles were redox active, however addition of the guest did not influence the redox potentials. 相似文献
5.
《Angewandte Chemie (International ed. in English)》2017,56(18):4930-4935
By employing the subcomponent self‐assembly approach utilizing 5,10,15,20‐tetrakis(4‐aminophenyl)porphyrin or its zinc(II) complex, 1H ‐4‐imidazolecarbaldehyde, and either zinc(II) or iron(II) salts, we were able to prepare O‐symmetric cages having a confined volume of ca. 1300 Å3. The use of iron(II) salts yielded coordination cages in the high‐spin state at room temperature, manifesting spin‐crossover in solution at low temperatures, whereas corresponding zinc(II) salts led to the corresponding diamagnetic analogues. The new cages were characterized by synchrotron X‐ray crystallography, high‐resolution mass spectrometry, and NMR, Mössbauer, IR, and UV/Vis spectroscopy. The cage structures and UV/Vis spectra were independently confirmed by state‐of‐the‐art DFT calculations. A remarkably high‐spin‐stabilizing effect through encapsulation of C70 was observed. The spin‐transition temperature T 1/2 is lowered by 20 K in the host–guest complex. 相似文献
6.
7.
Two mixed ligand ZnII complexes [Zn(phen)L2/2](H2L) ( 1 ) and [(phen)2Zn(μ‐L)Zn(phen)2]L � 11H2O ( 2 ) with H2L = suc‐cinic acid were prepared and crystallographically characterized. Complex 1 crystallizes in the monoclinic space group C2/c (no. 15) with a = 13.618(1) Å, b = 9.585(1) Å, c = 15.165(1) Å, β = 96.780(6)°, V = 1965.6(3)Å3, Z = 4 and complex 2 in the triclinic space group P 1¯ (no. 2) with a = 12.989(2)Å, b = 14.464(2)Å, c = 18.025(3)Å, α = 90.01(1)°, β = 109.69(1)°, γ = 112.32(1)°, V = 2917.4(8) Å3, Z = 2. 1 consists of succinic acid molecules and 1D zigzag [Zn(phen)(C4H4O4)2/2] polymeric chains, in which the tetrahedrally coordinated Zn atoms are bridged by bis ‐ monodentate succinato ligands. Succinic acid molecules play an important role in supramolecular assemblies of the polymeric chains into 2D layers as well as in the stacking of 2D layers. 2 is composed of [(phen)2Zn(μ‐L)Zn(phen)2]2+ complex cations, succinate anions and hydrogen bonded water molecules. Within the divalent cations, Zn atoms are octahedrally coordinated by four N atoms of two phen ligands and two O atoms of one bis‐chelating succinato ligand. Through the intermolecular π—π stacking interactions, the complex cations form positively charged 2D layers, between which the noncoordinating succinate anions and water molecules are sandwiched. 相似文献
8.
《化学:亚洲杂志》2017,12(24):3203-3207
The self‐assembly process of a Pd12L24 sphere was revealed by a quantitative approach (quantitative analysis of self‐assembly process: QASAP) quantifying all the substrates, the products, and the observable intermediates, indicating that the Pd12L24 sphere is produced through several pathways. Firstly, Pdn L2n (n= 6, 8, and 9), which are perfectly closed structures smaller than the Pd12L24 sphere, and a mixture of intermediates not observed by NMR ( Int ) were produced. Next, the sphere was assembled from intra‐/intermolecular reaction of a certain class of Int (path A) and from the coordination of free pyridyl groups in Int to the PdII center of Pdn L2n (n= 6, 8, and 9) (path B). While capping the free pyridyl groups in Int with PdII ions perfectly inhibited the sphere formation, the addition of free L to Int accelerated the formation of the sphere. 相似文献
9.
Xuedong Xiao Hongbo Chen Xuxu Dong Dazhuo Ren Qiang Deng Dapeng Wang Wei Tian 《Angewandte Chemie (International ed. in English)》2020,59(24):9534-9541
The cation–π interaction is a strong non‐covalent interaction that can be used to prepare high‐strength, stable supramolecular materials. However, because the molecular plane of a cation‐containing group and that of aromatic structure are usually perpendicular when forming a cation–π complex, it is difficult to exploit the cation–π interaction to prepare a 2D self‐assembly in which the molecular plane of all the building blocks are parallel. Herein, a double cation–π‐driven strategy is proposed to overcome this difficulty and have prepared 2D self‐assemblies with long‐range ordered molecular hollow hexagons. The double cation–π interaction makes the 2D self‐assemblies stable. The 2D self‐assemblies are to be an effective carrier that can eliminate metal‐nanoparticle aggregation. Such 2D assembly/palladium nanoparticle hybrids are shown to exhibit recyclability and superior catalytic activity for a model reaction. 相似文献
10.
Two‐Component Self‐Assembly: Hierarchical Formation of pH‐Switchable Supramolecular Networks by π–π Induced Aggregation of Ion Pairs
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Krishnananda Samanta Martin Ehlers Prof. Dr. Carsten Schmuck 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(43):15242-15247
Two‐component self‐assembly is a promising approach to construct functional nanomaterials. Interaction of a flexible guanidiniocarbonyl pyrrole tetra‐cation ( 1 ) with naphthalene diimide dicarboxylic acid (NDIDC) in aqueous DMSO leads to the formation of supramolecular networks. First, the carboxylate groups of NDIDC bind to the guanidiniocarbonyl pyrrole cations of 1 in a 1:2 stoichiometry. Further π–π induced aggregation then leads to 3D networks, as established by dynamic light scattering studies (DLS), NMR, fluorescence titration, viscosity measurements, AFM, and TEM microscopy. Due to ion pairing, the resulting aggregates can be switched between the monomers and the aggregates reversibly using external stimuli like protonation or deprotonation. At high concentration, a stable colloidal solution is formed, which shows an extensive Tyndall effect. Increasing the concentrations even further leads to formation of a supramolecular gel. 相似文献
11.
Leonardo C. Ferreira Carlos A. L. Filgueiras Prof. Dr. Lorenzo C. Visentin Jairo Bordinhaõ Manfredo Hörner 《无机化学与普通化学杂志》2009,635(8):1225-1230
The preparation and spectroscopic and structural characterization of three ZnII complexes with bis[N‐(2,6‐dimethylphenyl)imine]acenaphthene, L1, and with bis[N‐(2‐ethylphenyl)imine]acenaphthene, L2, are decribed herein. Two of the complexes were prepared from ZnCl2 and the third from Zn(NCS)2. One‐pot reaction techniques were used, leading to high yields. The complexes were characterized by microanalysis, IR and 1H NMR spectroscopy, and single‐crystal X‐ray diffraction. The structures of the complexes are significantly different, with the chloride‐containing species forming distorted tetrahedra around the metal, whereas its thiocyanate analog is dimeric, with each metal at the center of a distorted square pyramid, with bridging and terminal [SCN]– ligands. 相似文献
12.
Divya S. Philips Kalathil K. Kartha Antiope T. Politi Timo Krüger Rodrigo Q. Albuquerque Gustavo Fernndez 《Angewandte Chemie (International ed. in English)》2019,58(14):4732-4736
Cooperative π–π interactions and H‐bonding are frequently exploited in supramolecular polymerization; however, close scrutiny of their mutual interplay has been largely unexplored. Herein, we compare the self‐assembly behavior of a series of C2‐ and C3‐symmetrical oligophenyleneethynylenes differing in their amide topology (N‐ or C‐centered). This subtle structural modification brings about drastic changes in their photophysical and supramolecular properties, highlighting the reciprocal impact of H‐bonding vs. preorganization on the evolution and final outcome of supramolecular systems. 相似文献
13.
[Cu(C12H8N2)(C4H4O4)(H2O)]2 · C4H6O4 was prepared by the reaction of succinic acid, CuCl2 · 2 H2O, 1,10‐phenanthroline (phen = C12H8N2), and Na2CO3 in a CH3OH–H2O solution. The crystal structure (triclinic, P 1 (no. 2), a = 7.493(1), b = 9.758(1), c = 13.517(1) Å; α = 68.89(1)°, β = 88.89(1)°, γ = 73.32(1)°, Z = 1, R = 0.0308, wR2 = 0.0799 for 3530 observed reflections (F ≥ 2σ(F ) out of 3946 unique reflections) consists of hydrogen bonded succinic acid molecules and succinato bridged 1 D zipperlike supramolecular [Cu(phen)(C4H4O4)2/2(H2O)]2 double chains based on 1 D π‐π stacking interactions between the chelating phen systems at distances of 3.71 Å and 3.79 Å. The Cu atoms are fivefold trigonal bipyramidally coordinated by two N atoms of the bidentate chelating phen ligand and three O atoms of one water molecule and two bidentate bridging succinate ligands. The water O atom and one phen N atom are at the apical positions (equatorial: d(Cu–O) = 1.945, 2.254(2) Å, d(Cu–N) = 2.034(2) Å; axial: d(Cu–O) = 1.971(2) Å, d(Cu–N) = 1.995 Å). 相似文献
14.
Porphyrin–AuIII complexes, which were partially or totally modified with C6F5 at the meso positions, were synthesized. The highly electron‐withdrawing substituents induced electron‐deficient states and Lewis acid properties. Single‐crystal X‐ray analysis of the ion pairs revealed ion‐pairing assemblies with characteristics dependent on the number and substitution pattern of the C6F5 units and the geometries of the anions. 相似文献
15.
The blue copper complex compounds [Cu(phen)2(C6H8O4)] · 4.5 H2O ( 1 ) and [(Cu2(phen)2Cl2)(C6H8O4)] · 4 H2O ( 2 ) were synthesized from CuCl2, 1,10‐phenanthroline (phen) and adipic acid in CH3OH/H2O solutions. [Cu(phen)2‐ (C6H8O4)] complexes and hydrogen bonded H2O molecules form the crystal structure of ( 1 ) (P1 (no. 2), a = 10.086(2) Å, b = 11.470(2) Å, c = 16.523(3) Å, α = 99.80(1)°, β = 115.13(1)°, γ = 115.13(1)°, V = 1617.5(5) Å3, Z = 2). The Cu atoms are square‐pyramidally coordinated by four N atoms of the phen ligands and one O atom of the adipate anion (d(Cu–O) = 1.989 Å, d(Cu–N) = 2.032–2.040 Å, axial d(Cu–N) = 2.235 Å). π‐π stacking interactions between phen ligands are responsible for the formation of supramolecular assemblies of [Cu(phen)2(C6H8O4)] complex molecules into 1 D chains along [111]. The crystal structure of ( 2 ) shows polymeric [(Cu2(phen)2Cl2)(C6H8O4)2/2] chains (P1 (no. 2), a = 7.013(1) Å, b = 10.376(1) Å, c = 11.372(3) Å, α = 73.64(1)°, β = 78.15(2)°, γ = 81.44(1)°, V = 773.5(2) Å3, Z = 1). The Cu atoms are fivefold coordinated by two Cl atoms, two N atoms of phen ligands and one O atom of the adipate anion, forming [CuCl2N2O] square pyramids with an axial Cl atom (d(Cu–O) = 1.958 Å, d(Cu–N) = 2.017–2.033 Å, d(Cu–Cl) = 2.281 Å; axial d(Cu–Cl) = 2.724 Å). Two square pyramids are condensed via the common Cl–Cl edge to centrosymmetric [Cu2Cl2N4O2] dimers, which are connected via the adipate anions to form the [(Cu2(phen)2Cl2)(C6H8O4)2/2] chains. The supramolecular 3 D network results from π‐π stacking interactions between the chains. H2O molecules are located in tunnels. 相似文献
16.
The title compound [Cu2(phen)2(C9H14O4)2] · 6 H2O was prepared by the reaction of CuCl2 · 2 H2O, 1,10‐phenanthroline (phen), azelaic acid and Na2CO3 in a CH3OH/H2O solution. The crystal structure (monoclinic, C2/c (no. 15), a = 22.346(3), b = 11.862(1), c = 17.989(3) Å, β = 91.71(1)°, Z = 4, R = 0.0473, wR2 = 0.1344 for 4279 observed reflections) consists of centrosymmetric dinuclear [Cu2(phen)2(C9H14O4)2] complexes and hydrogen bonded H2O molecules. The Cu atom is square‐planar coordinated by the two N atoms of the chelating phen ligand and two O atoms of different bidentate bridging azelaate groups with d(Cu–N) = 2.053, 2.122(2) Å and d(Cu–O) = 1.948(2), 2.031(2) Å. Two azelaate anions bridge two common Cu atoms via the terminal O atoms (d(C–O) = 1.29(2) Å; d(C–C) = 1.550(4)–1.583(4) Å). Phen ligands of adjacent complexes cover each other at distances of about 3.62 Å, indicating π‐π stacking interaction, by which the complexes are linked to 1 D bands. 相似文献
17.
18.
The tris‐bidentate complex [Ni(C12H8N2)2(CO3)] was synthesized by the reaction of Na2CO3, 1,10‐phenanthroline (phen = C12H8N2) and NiSO4 · 6 H2O in the presence of succinic acid in a CH3OH–H2O solution. The compound crystallizes as heptahydrate. The crystal structure (monoclinic, P21/c (no. 14), a = 9.897(1), b = 26.384(2), c = 10.582(1) Å, β = 105.87(1)°, Z = 4, R = 0.0505, wR2 = 0.1029 for 3166 observed reflections (F ≥ 2σ(F ) out of 6100 unique reflections) consists of hydrogen bonded water molecules and [Ni(phen)2(CO3)] complex molecules. The Ni atoms are sixfold octahedrally coordinated by the four N atoms of two bidentate chelating phen ligands and by two O atoms of the bidentate chelating carbonate group with d(Ni–N) = 2.092–2.100 Å, d(Ni–O) = 2.051, 2.079 Å. The complex molecules are stacked into 2D corrugated layers parallel to (010) via two types of intermolecular π‐π stacking interactions. One occurs between two quinoline rings of neighboring phen ligands at the distance of 3.63 Å in [010] direction and the other results from 1D π‐π stacking interactions through partially covered phen rings at alternative distances of 3.26 Å and 3.33 Å in [001] direction. The water molecules are sandwiched between 2D layers. 相似文献
19.
Construction of Hetero‐Four‐Layered Tripalladium(II) Cyclophanes by Transannular π⋅⋅⋅π Interactions
下载免费PDF全文
![点击此处可从《Angewandte Chemie (International ed. in English)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Haeri Lee Dr. Tae Hwan Noh Prof. Dr. Ok‐Sang Jung 《Angewandte Chemie (International ed. in English)》2016,55(3):1005-1009
A synthetic strategy for the generation of new molecular species utilizing a provision of nature is presented. Nano‐dimensional (23(2)×21(1)×16(1) Å3) hetero‐four‐layered trimetallacyclophanes were constructed by proof‐of‐concept experiments that utilize a suitable combination of π???π interactions between the central aromatic rings, tailor‐made short/long spacer tridentate donors, and the combined helicity. The behavior of the unprecedented four‐layered metallacyclophane system offers a landmark in the development of new molecular systems. 相似文献
20.
Reaction of MnSO4 · H2O, 2,2′‐bipyridine (bpy), suberic acid and Na2CO3 in CH3OH/H2O yielded a mixture of [Mn2(H2O)4(bpy)2(C8H12O4)2] · 2 H2O ( 1 ) and [Mn(H2O)2‐ (bpy)(C8H12O4)2/2] · H2O ( 2 ). In both complexes, the Mn atoms are octahedrally coordinated by two N atoms of one bpy ligand and four O atoms of two trans positioned H2O molecules and two suberato ligands (d(Mn–O) = 2.107–2.328 Å; d(Mn–N) = 2.250–2.330 Å). The bis‐monodentate suberato ligands bridge Mn atoms to form dinuclear [Mn2(H2O)4(bpy)2(C8H12O4)2] complex molecules in 1 and 1D [Mn(H2O)2(bpy)(C8H12O4)2/2] chains in 2 . Via the intermolecular hydrogen bondings and π‐π stacking interactions, the dinuclear molecules in 1 are assembled into 2D networks parallel to (100), between which the crystal H2O molecules are sandwiched. The polymeric chains in 2 are linked together by interchain hydrogen bonding and π‐π stacking interactions into 3D networks with the crystal H2O molecules located in tunnels along [010]. Crystal data for 1 : P21/c (no. 14), a = 10.092(1) Å, b = 11.916(2) Å, c = 17.296(2) Å, β = 93.41(1)° and Z = 2. Crystal data for 2 : P21/c (no. 14), a = 11.176(2) Å, b = 9.688(1) Å, c = 37.842(6) Å, β = 90.06(1)° and Z = 8. 相似文献