Chiral Supramolecular Nanotubes of Single-Chain Magnets

We report a single-chain magnet (SCM) made of a terbium(III) building block and a nitronyl-nitroxide radical (NIT) functionalized with an aliphatic chain. This substitution is targeted to induce a long-range distortion of the polymeric chain and accordingly it gives rise to chains that are curled with almost 20 nm helical pitch. They self-organize as a chiral tubular superstructure made of 11 chains wound around each other. The supramolecular tubes have a 4.5 nm internal diameter. Overall, this forms a porous chiral network with almost 44 % porosity. Ab initio calculations highlight that each Tb^III ion possesses high magnetic anisotropy. Indeed, notwithstanding the supramolecular arrangement each chain behaves as a SCM. Magnetic relaxation with both finite and infinite-size regimes is observed and confirms the validity of the Ising approximation. This is associated with quite strong coercive field and magnetic remanence (H_c=2400 Oe M_R=2.09 μ_B at 0.5 K) for this class of compounds.     

Three‐Dimensional Antiferromagnetic Order of Single‐Chain Magnets: A New Approach to Design Molecule‐Based Magnets

Two one‐dimensional compounds composed of a 1:1 ratio of Mn^III salen‐type complex and Ni^II oximato moiety with different counter anions, PF₆^? and BPh₄^?, were synthesized: [Mn(3,5‐Cl₂saltmen)Ni(pao)₂(phen)]PF₆ ( 1 ) and [Mn(5‐Clsaltmen)Ni(pao)₂(phen)]BPh₄ ( 2 ), where 3,5‐Cl₂saltmen^2?=N,N′‐(1,1,2,2‐tetramethylethylene)bis(3,5‐dichlorosalicylideneiminate); 5‐Clsaltmen^2?=N,N′‐(1,1,2,2‐tetramethylethylene)bis(5‐chlorosalicylideneiminate); pao^?=pyridine‐2‐aldoximate; and phen=1,10‐phenanthroline. Single‐crystal X‐ray diffraction study was carried out for both compounds. In 1 and 2 , the chain topology is very similar forming an alternating linear chain with a [‐Mn^III‐ON‐Ni^II‐NO‐] repeating motif (where ‐ON‐ is the oximate bridge). The use of a bulky counteranion, such as BPh₄^?, located between the chains in 2 rather than PF₆^? in 1 , successfully led to the magnetic isolation of the chains in 2 . This minimization of the interchain interactions allows the study of the intrinsic magnetic properties of the chains present in 1 and 2 . While 1 and 2 possess, as expected, very similar paramagnetic properties above 15 K, their ground state is antiferromagnetic below 9.4 K and paramagnetic down to 1.8 K, respectively. Nevertheless, both compounds exhibit a magnet‐type behavior at temperatures below 6 K. While for 2 , the observed magnetism is well explained by a Single‐Chain Magnet (SCM) behavior, the magnet properties for 1 are induced by the presence in the material of SCM building units that order antiferromagnetically. By controlling both intra‐ and interchain magnetic interactions in this new [Mn^IIINi^II] SCM system, a remarkable AF phase with a magnet‐type behavior has been stabilized in relation with the intrinsic SCM properties of the chains present in 1 . This result suggests that the simultaneous enhancement of both intrachain (J) and interchain (J′) magnetic interactions (with keeping J ? J′), independently of the presence of AF phase might be an efficient route to design high temperature SCM‐based magnets.     

Cyano‐Bridged MnIII?MIII Single‐Chain Magnets with MIII=CoIII,FeIII, MnIII,and CrIII

A series of isostructural cyano‐bridged Mn^III(h.s.)–M^III(l.s.) alternating chains, [Mn^III(5‐TMAMsalen)M^III(CN)₆] ? 4H₂O (5‐TMAMsalen^2?=N,N′‐ethylenebis(5‐trimethylammoniomethylsalicylideneiminate), Mn^III(h.s.)=high‐spin Mn^III, M^III(l.s.)=low‐spin Co^III, Mn? Co ; Fe^III, Mn? Fe ; Mn^III, Mn? Mn ; Cr^III, Mn? Cr ) was synthesized by assembling [Mn^III(5‐TMAMsalen)]³⁺ and [M^III(CN)₆]^3?. The chains present in the four compounds, which crystallize in the monoclinic space group C2/c, are composed of an [‐Mn^III‐NC‐M^III‐CN‐] repeating motif, for which the ‐NC‐M^III‐CN‐ motif is provided by the [M^III(CN)₆]^3? moiety adopting a trans bridging mode between [Mn^III(5‐TMAMsalen)]³⁺ cations. The Mn^III and M^III ions occupy special crystallographic positions: a C₂ axis and an inversion center, respectively, forming a highly symmetrical chain with only one kind of cyano bridge. The Jahn–Teller axis of the Mn^III(h.s.) ion is perpendicular to the N₂O₂ plane formed by the 5‐TMAMsalen tetradentate ligand. These Jahn–Teller axes are all perfectly aligned along the unique chain direction without a bending angle, although the chains are corrugated with an Mn‐N_axis‐C angle of about 144°. In the crystal structures, the chains are well separated with the nearest inter‐chain M???M distance being relatively large at 9 Å due to steric hindrance of the bulky trimethylammoniomethyl groups of the 5‐TMAMsalen ligand. The magnetic properties of these compounds have been thoroughly studied. Mn? Fe and Mn? Mn display intra‐chain ferromagnetic interactions, whereas Mn? Cr is characterized by an antiferromagnetic exchange that induces a ferrimagnetic spin arrangement along the chain. Detailed analyses of both static and dynamic magnetic properties have demonstrated without ambiguity the single‐chain magnet (SCM) behavior of these three systems, whereas Mn? Co is merely paramagnetic with S_Mn=2 and D/k_B=?5.3 K (D being a zero‐field splitting parameter). At low temperatures, the Mn? M compounds with M=Fe, Mn, and Cr display remarkably large M versus H hysteresis loops for applied magnetic fields along the easy magnetic direction that corresponds to the chain direction. The temperature dependence of the associated relaxation time for this series of compounds systematically exhibits a crossover between two Arrhenius laws corresponding to infinite‐chain and finite‐chain regimes for the SCM behavior. These isostructural hetero‐spin SCMs offer a unique series of alternating [‐Mn‐NC‐M‐CN‐] chains, enabling physicists to test theoretical SCM models between the Ising and Heisenberg limits.     

Coulombic interactions,hydrogen bonding and supramolecular chirality in pyridinium trifluoromethanesulfonate

The title compound, C₅H₆N⁺·CF₃SO₃⁻, was serendipitously crystallized in the chiral space group P4₃2₁2. The component entities associate into hydrogen‐bonded helical chains, which propagate along the a and b axes of the crystal, with an alternating disposition of the cations and anions along the chain. N—H...O charge‐assisted hydrogen bonds, from each pyridinium cation to two adjacent trifluoromethanesulfonate anions and from every anion to two different cations, direct the formation of the supramolecular chiral arrays. The crystal packing exhibits nonconventional C—H...O and C—H...F hydrogen bonds between the components. The observed structure demonstrates induction of supramolecular chirality by a combination of Coulombic attractions and intermolecular hydrogen bonds.     

Distinct chiral units from an axially prochiral ligand in a photoluminescent zinc(II)–organic complex

The asymmetric unit of the title compound, poly[(dimethylamine‐κN)[μ₃‐(E)‐2,6‐dimethyl‐4‐styrylpyridine‐3,5‐dicarboxylato‐κ³O³:O^3′:O⁵]zinc(II)], [Zn(C₁₇H₁₃NO₄)(C₂H₇N)]_n, consists of one crystallographically independent distorted tetrahedral Zn^II cation, one (E)‐2,6‐dimethyl‐4‐styrylpyridine‐3,5‐dicarboxylate (mspda²⁻) ligand and one coordinated dimethylamine molecule. Two S‐ and R‐type chiral units are generated from the axially prochiral mspda²⁻ ligand through C—H...O hydrogen bonds. The R‐type chiral units assemble a left‐handed (M) Zn–mspda helical chain, while the right‐handed (P) Zn–mspda helical chain is constructed from neighbouring S‐type chiral units. The P‐ and M‐type helical chains are interlinked by carboxylate O atoms to form a one‐dimensional ladder. Interchain N—H...O hydrogen bonds extend these one‐dimensional ladders into a two‐dimensional supramolecular architecture. The title compound exhibits luminescence at λ_max = 432 nm upon excitation at 365 nm.     

Hydro­gen‐bonded supramolecular motifs in 4,4′‐bipyridinium 8‐hydroxy‐7‐iodo­quinoline‐5‐sulfonate dihydrate

In the title compound, C₁₀H₉N₂⁺·C₉H₅INO₄S⁻·2H₂O, the 4,4′‐bi­pyridine mol­ecule is protonated at one of the pyridine N atoms. These moieties self‐assemble into a supramolecular chain along the a axis through N—H⋯N hydrogen bonds. The quinolinol OH group acts as a donor with respect to a sulfonate O atom [O—H⋯O(sulfonate)] and acts as an acceptor with respect to a C—H group of ferron [C—H⋯O(hydroxy)], forming a supramolecular chain along the b axis. These two types of supramolecular chains (one type made up of bi­pyridine motifs and the other made up of sulfoxine motifs) interact viaπ–π stacking, generating a three‐dimensional framework. These chains are further crosslinked by C—­H⋯O hydrogen bonds and O—H⋯O hydrogen bonds involving water mol­ecules.     

Thioamides: Versatile Bonds To Induce Directional and Cooperative Hydrogen Bonding in Supramolecular Polymers

The amide bond is a versatile functional group and its directional hydrogen‐bonding capabilities are widely applied in, for example, supramolecular chemistry. The potential of the thioamide bond, in contrast, is virtually unexplored as a structuring moiety in hydrogen‐bonding‐based self‐assembling systems. We report herein the synthesis and characterisation of a new self‐assembling motif comprising thioamides to induce directional hydrogen bonding. N,N′,N′′‐Trialkylbenzene‐1,3,5‐tris(carbothioamide)s (thioBTAs) with either achiral or chiral side‐chains have been readily obtained by treating their amide‐based precursors with P₂S₅. The thioBTAs showed thermotropic liquid crystalline behaviour and a columnar mesophase was assigned. IR spectroscopy revealed that strong, three‐fold, intermolecular hydrogen‐bonding interactions stabilise the columnar structures. In apolar alkane solutions, thioBTAs self‐assemble into one‐dimensional, helical supramolecular polymers stabilised by three‐fold hydrogen bonding. Concentration‐ and temperature‐dependent self‐assembly studies performed by using a combination of UV and CD spectroscopy demonstrated a cooperative supramolecular polymerisation mechanism and a strong amplification of supramolecular chirality. The high dipole moment of the thioamide bond in combination with the anisotropic shape of the resulting cylindrical aggregate gives rise to sufficiently strong depolarised light scattering to enable depolarised dynamic light scattering (DDLS) experiments in dilute alkane solution. The rotational and translational diffusion coefficients, D_trans and D_rot, were obtained from the DDLS measurements, and the average length, L, and diameter, d, of the thioBTA aggregates were derived (L=490 nm and d=3.6 nm). These measured values are in good agreement with the value L_w=755 nm obtained from fitting the temperature‐dependent CD data by using a recently developed equilibrium model. This experimental verification validates our common practice for determining the length of BTA‐based supramolecular polymers from model fits to experimental CD data. The ability of thioamides to induce cooperative supramolecular polymerisation makes them effective and broadly applicable in supramolecular chemistry.     

新颖有机/无机杂化配位聚合物[(DBU-H)(PbI3)]n的合成、晶体结构和量子化学研究

The coordination polymer [（DBU-H）（PbI3）]n（DBU=catena-（1,8-diazabicyclo[5,4,0]-undec-7-ene） was synthesized by self-assembly reaction of DBU and PbI2 at room temperature with pH=6.0 and structurally characterized by means of X-ray single crystal diffraction. It crystallizes in monoclinic system with space group P21/c and crystal parameters a = 1.1940（2） nm, b = 1.7409（4） nm, c = 0.81347（16） nm, β= 100.32（3）°, chemical formula C9H17N213Pb and Mr=741.15, V= 1.6635（6） nm^3, Z=4, Dc=2.959 g/cm^3, F（000）= 1304,μ（Mo Kα）= 15.687 mm^-1, the final R=0.0389 and wR=0.0635 for 2279 observed reflections with 1〉2σ（I）. Structure analysis shows that the inorganic anion chain consists of distorted PbI6 octahedra, which shares the same faces with adjacent PbI6 units to form one-dimensional infinite chains along the c-axis. Anion chains are surrounded by protonated （DBU-H）^＋ cations. Anion chains and cations are in combination with each other by static attracting forces in the crystal to form so-called organic-inorganic hybrid structure. According to the crystal structure data, quantum chemical calculation with DFT at B3LYP level was used to reveal the electronic structure of title compound.     

A Uranium‐Based UO2+–Mn2+ Single‐Chain Magnet Assembled trough Cation–Cation Interactions

Single‐chain magnets (SCMs) are materials composed of magnetically isolated one‐dimensional (1D) units exhibiting slow relaxation of magnetization. The occurrence of SCM behavior requires the fulfillment of stringent conditions for exchange and anisotropy interactions. Herein, we report the synthesis, the structure, and the magnetic characterization of the first actinide‐containing SCM. The 5f–3d heterometallic 1D chains [{[UO₂(salen)(py)][M(py)₄](NO₃)}]_n, (M=Cd ( 1 ) and M=Mn ( 2 ); py=pyridine) are assembled trough cation–cation interaction from the reaction of the uranyl(V) complex [UO₂(salen)py][Cp*₂Co] (Cp*=pentamethylcyclopentadienyl) with Cd(NO₃)₂ or Mn(NO₃)₂ in pyridine. The infinite UMn chain displays a high relaxation barrier of 134±0.8 K (93±0.5 cm^?1), probably as a result of strong intra‐chain magnetic interactions combined with the high Ising anisotropy of the uranyl(V) dioxo group. It also exhibits an open magnetic hysteresis loop at T<6 K, with an impressive coercive field of 3.4 T at 2 K.     

Mirror helices and helicity switch at surfaces based on chiral triangular-shape oligo(phenylene ethynylenes)

The self‐assembly of triangular‐shaped oligo(phenylene ethynylenes) (OPEs), peripherally decorated with chiral and linear paraffinic chains, is investigated in bulk, onto surfaces and in solution. Whilst the X‐ray diffraction data for the chiral studied systems display a broad reflection centered at 2θ ～20° (λ=Cu_Kα), the higher crystallinity of OPE 3 , endowed with three linear decyl chains, results in a diffractrogram with a number of well‐resolved reflections that can be accurately indexed as a columnar packing arranged in 2D oblique cells. Compounds (S)‐ 1 a and (R)‐ 1 b —endowed with (S)‐ and (R)‐3,7‐dimethyloctyloxy chains—transfer their chirality to the supramolecular structures formed upon their self‐assembly, and give rise to helical nanostructures of opposite handedness. A helicity switch is noticeable for the case of chiral (S)‐ 2 decorated with (S)‐2‐methylnonyloxy chains which forms right‐handed helices despite it possesses the same stereoconfiguration for their stereogenic carbons as (S)‐ 1 a that self‐assembles into left‐handed helices. The stability and the mechanism of the supramolecular polymerization in solution have been investigated by UV/Vis experiments in methylcyclohexane. These studies demonstrate that the larger the distance between the stereogenic carbon and the aromatic framework is, the more stable the aggregate is. Additionally, the self‐assembly mechanism is conditioned by the peripheral substituents: whereas compounds (S)‐ 1 a and (R)‐ 1 b self‐assemble in a cooperative manner with a low degree of cooperativity, the aggregation of (S)‐ 2 and 3 is well described by an isodesmic model. Therefore, the interaction between the chiral coil chains conditions the handedness of the helical pitch, the stability of the supramolecular structure and the supramolecular polymerization mechanism of the studied OPEs.     

Crystal Structure, Thermal Analysis and Theoretical Calculation of a One-dimensional Chain Complex [Zn（dafo）2（H2O）2]（NO3）2

Introduction Molecular recognition and molecular self-assemblycarried out by cooperation of the weak interactions(electrostatic reaction, hydrogen bonds, van der Waalsforce, short-range repulsive force, etc) are the commonphenomena in nature. In recent years, the research onsupramolecular complex has been a crossing focus ofseveral subjects such as chemistry, physics, biology,material and information.1 Supramolecular complex hasa wide application foreground in material, catalysis,conductor,…     

Synthesis and Crystal Structure of 1D Coordination Polymer of N,N＇-Bis（3-pyridylmethyl）-1,4-benzenedicarboxamide and Cobalt（Ⅱ） Nitrate

A noval cobalt(II) coordination polymer, {[Co(bpmb)(H₂O)₂(C₂H₅OH)₂]·(NO₃)₂}‐ (1). where bpmb=N,N′‐bis(3‐pyridylmethyl)‐1,4‐benzenedicarboxamide, was synthesized by self‐assembly of the two topic ligands with cobalt nitrate in ethanol solution, and characterized structurally by X‐ray crystallography analysis. The crystal data belong to triclinic, space group P1 with cell parameters a=0.8911(3) nm, b=0.9042(3) nm, c= 1.0068(3) nm, α= 73.083(5)°, β=81.069(5)°, γ=76.210(5)°, R₁=0.0518, wR₂=0.0947. The results of structure analysis indicate that each bpmb ligand coordinates two Co(II) atoms and each metal atom is in octahedral coordination geometry with four oxygen atoms of two ethanol and two water molecules, two nitrogen atoms from two different bpmb ligands in trans position forming an infinite 1D chain‐like structure. There BTC hydrogen bonding and π‐π stacking interaction among these chains, leading to supramolecular formation with 3D net structure.     

Synthesis,structure and characterization of two copper(II) supramolecular coordination polymers based on a multifunctional ligand 2‐amino‐4‐sulfobenzoic acid

Copper(II) coordination polymers have attracted considerable interest due to their catalytic, adsorption, luminescence and magnetic properties. The reactions of copper(II) with 2‐amino‐4‐sulfobenzoic acid (H₂asba) in the presence/absence of the auxiliary chelating ligand 1,10‐phenanthroline (phen) under ambient conditions yielded two supramolecular coordination polymers, namely (3‐amino‐4‐carboxybenzene‐1‐sulfonato‐κO¹)bis(1,10‐phenanthroline‐κ²N,N′)copper(II) 3‐amino‐4‐carboxybenzene‐1‐sulfonate monohydrate, [Cu(C₇H₆N₂O₅S)(C₁₂H₈N₂)₂](C₇H₆N₂O₅S)·H₂O, (1), and catena‐poly[[diaquacopper(II)]‐μ‐3‐amino‐4‐carboxylatobenzene‐1‐sulfonato‐κ²O⁴:O^4′], [Cu(C₇H₆N₂O₅S)(H₂O)₂]_n, (2). The products were characterized by FT–IR spectroscopy, thermogravimetric analysis (TGA), solid‐state UV–Vis spectroscopy and single‐crystal X‐ray diffraction analysis, as well as by variable‐temperature powder X‐ray diffraction analysis (VT‐PXRD). Intermolecular π–π stacking interactions in (1) link the mononuclear copper(II) cation units into a supramolecular polymeric chain, which is further extended into a supramolecular double chain through interchain hydrogen bonds. Supramolecular double chains are then extended into a two‐dimensional supramolecular double layer through hydrogen bonds between the lattice Hasba⁻ anions, H₂O molecules and double chains. Left‐ and right‐handed 2₁ helices formed by the Hasba⁻ anions are arranged alternately within the two‐dimensional supramolecular double layers. Complex (2) exhibits a polymeric chain which is further extended into a three‐dimensional supramolecular network through interchain hydrogen bonds. Complex (1) shows a reversible dehydration–rehydration behaviour, while complex (2) shows an irreversible dehydration–rehydration behaviour.     

One-dimensional end-to-end azide-bridged Mn(III) complexes incorporating alkali metal ions: slow magnetic relaxations and metamagnetism

Three azide‐bridged Mn^III chains [Mn(3‐MeOsalpn)(N₃)] ? 0.5 AClO₄ (A=Na ( 1 ), K ( 2 ), Rb ( 3 ); 3‐MeOsalpn=N,N′‐propylenebis(3‐methoxysalicylideneiminato) dianion) incorporating alkali metal ions and perchlorate anions were systematically synthesized. The overall structure can be described as a one‐dimensional chain bridged by end‐to‐end azide ligands, although spatial arrangements of Jahn–Teller axes of Mn in 1 and 2 are different from that in 3 . Relying on the alkali metal ions, magnetic properties are varied from a two‐step phase transition ( 1 ) to metamagnetic transitions ( 2 and 3 ). In this system, spin canting definitely plays a central role in giving rise to the apparent slow magnetic relaxations in 1 and 2 because application of a high external magnetic field tends to destroy single‐chain magnet (SCM) properties. Despite the existence of a long‐range antiferromagnetic order at T_N, slow magnetic relaxation is notably observed in 2 , which likely emanates from the operative spin canting below T_N.     

Synthesis,Crystal Structure,Vibrational Spectroscopy and Thermal Behavior of the First Alkali Metal Hydrated Hexaborate： K2[B6O9（OH）2]

New hydrated potassium hexaborate K2[B6O9（OH）2] has been synthesized under mild solvothermal conditions. The structure was determined by single-crystal X-ray diffraction and further characterized by FT-IR, Rarnan spectra and DTA-TG. It crystallizes in the monoclinic system with space group P21/n, a=0.9036（2） nm, b=0.66052（18） nm, c=1.5997（4） nm, β=91.862（4）°, V=0.9543（4） nm^3 and Z=4. Its crystal structure consists of K-O polyhedra and 1-D stepped polyborate chains constructed by new [B6O9（OH）2]2- fundamental building blocks. 1-D polyborate chains contain 3,8-membered boron rings. Adjacent chains are further linked via H-bonding interactions into 2-D layers. The K^＋ cations reside not only between the layers but also in the 8-membered boron rings of the chains, compensating the negative charges of the borate chains and holding the layers together into the 3-D structure through bonding with oxygen atoms of the chains.     

Twist Grain Boundary Liquid‐Crystalline Phases under the Effect of the Magnetic Field: A Complete 2H and 13C NMR Study

A liquid crystal ( HZL 7/* ) containing an (S)‐2‐methylbutyl‐(S)‐lactate unit in the chiral chain, is investigated by means of ²H and ¹³C NMR spectroscopy in order to obtain information on its orientational order, its molecular structure and the effect of external magnetic fields on the supramolecular structure of its phases. This mesogen presents very peculiar mesomorphic properties and exhibits frustrated TGBA* and TGBC* phases in a wide temperature range up to 60 °C, as well as an additional phase transition from TGBC₁* to TGBC₂*. ²H NMR measurements show, for the first time, a peculiar magnetic field effect in unwinding the supramolecular structure of both the TGBA* and TGBC* phases. This effect is particularly evident at higher magnetic fields, while different behaviour is observed at lower magnetic fields. This indicates that the supramolecular structure is very sensitive to magnetic fields of the order of 1 Tesla. Moreover, the analysis of the ²H and ¹³C NMR spectra of HZL 7/* allow us to obtain several structural properties, such as the tilt angle of the TGBC* phases and the local orientational order parameters referred to the phenyl and biphenyl fragments. This is the first structural characterization of the frustrated phases of these complexes by means of NMR.     

Supramolecular Polymerization of C3‐Symmetric Organogelators: Cooperativity,Solvent, and Gelation Relationship

A systematic study of the influence of solvent and the size of C₃‐symmetric discotics on their supramolecular polymerization mechanism is presented. The cooperativity of the self‐assembly of the reported compounds is directly related to their gelation ability. The two series of C₃‐symmetric discotics investigated herein are based on benzene‐1,3,5‐tricarboxamides (BTAs) and oligo(phenylene ethynylene)‐based tricarboxamides (OPE? TAs) that are peripherally decorated with achiral ( 1 a and 2 a ) or chiral N‐(2‐aminoethyl)‐3,4,5‐trialkoxybenzamide units ( 1 b and 2 b ). The supramolecular polymerization of compounds 1 a , b and 2 a , b has been exhaustively investigated in a number of solvents and by using various techniques: variable‐temperature circular dichroism (VT‐CD) spectroscopy, concentration‐dependent ¹H NMR spectroscopy, and isothermal titration calorimetry (ITC). The supramolecular polymerization mechanism of compounds 2 is highly cooperative in solvents such as methylcyclohexane and toluene and is isodesmic in CHCl₃. Unexpectedly, chiral compound 1 b is practically CD‐silent, in contrast with previously reported BTAs. ITC measurements in CHCl₃ demonstrated that the supramolecular polymerization of BTA 1 a is isodesmic. These results confirm the strong influence of the π‐surface of the central aromatic core of the studied discotic and the branched nature of the peripheral side chains on the supramolecular polymerization. The gelation ability of these organogelators is negated in CHCl₃, in which the supramolecular polymerization mechanism is isodesmic.     

S=1/2 One‐Dimensional Random‐Exchange Ferromagnetic Zigzag Ladder,Which Exhibits Competing Interactions in a Critical Regime

The synthesis, crystal structure, and magnetic properties (from a combined experimental and First‐Principles Bottom‐Up theoretical study) of the new compound catena‐dichloro(2‐Cl‐3Mpy)copper(II), 1 , [2‐Cl‐3Mpy=2‐chloro‐3‐methylpyridine] are described and rationalized. Crystals of 1 present well isolated magnetic 1D chains (no 3D order was experimentally observed down to 1.8 K) and magnetic frustration stemming from competing ferromagnetic nearest‐neighbor (J_NN) interactions and antiferromagnetic next‐nearest neighbor (J_NNN) interactions, in which α=J_NNN/J_NN <?0.25. These magnetic interactions give rise to a unique magnetic topology: a two‐leg zigzag ladder composed of edge‐sharing up‐down triangles with antiferromagnetic interactions along the rails and ferromagnetic interactions along the zigzag chain that connects the rails. Crystals of 1 also present a random distribution of the 2‐Cl‐3Mpy groups, which are arranged in two different orientations, each with a 50 % occupancy. This translates into a random static structural disorder within each chain by virtue of which the value of the J_NN magnetic interactions can randomly take one of the following three values: 53, 36, and 16 cm^?1. The structural disorder does not affect the J_NNN value, which in all cases is approximately ?9 cm^?1. A proper statistical treatment of this disorder provides a computed magnetic susceptibility curve that reproduces the main features of the experimental data.     

Supramolecular Graft Copolymerization of a Polyester by Guest‐Selective Encapsulation of a Self‐Assembled Capsule

Repeating guest units of polyesters poly‐(R )‐ 2 were selectively encapsulated by capsule 1 (BF₄)₄ to produce supramolecular graft polymers. The encapsulation of the guest units was confirmed by ¹H NMR spectroscopy. The graft polymer structures were confirmed by the increase in the hydrodynamic radii and the solution viscosities of the polyesters upon complexation of the capsule. After the capsule was formed, atomic force microscopy showed extension of the polyester chains. The introduction of the graft chains onto poly‐(R )‐ 2 resulted in the main chain of the polymer having an M ‐helical morphology. The complexation of copolymers poly‐[(R )‐ 2 ‐co ‐(S )‐ 2 ] by the capsule gave rise to the unique chiral amplification known as the majority‐rules effect.     

1,1-环丁烷二羧酸单、双核铜配合物的合成、晶体结构、热分析和磁性

Two new copper complexes, [Cu（cbdc）（phen）（H2O）]·2H2O （1） and [Cu2（cbdc）（phen）2（H2O）2]（ClO4）2·H2O （2） （cbdc= 1,1-cyclobutanedicarboxylate and phen= 1,10-phenanthroline）, were synthesized by reaction of cbdc with Cu（ClO4）2 and phen in ethanol aqueous solution. Complex 1 crystallizes in monoclinic system with space group P2（1）/c and a=0.9428（4） nm, b= 1.2183（5） nm, c= 1.6265（7） nm, β= 102.418（5）°, V= 1.8246（13） nm^3, Z=4, R=0.0445, wR2=0.0947. The structure of 1 is discretely mononuclear, which is packed by π…π interaction forming a 3D supramolecular structure where Cu（Ⅱ） ion is five-coordinated and has square-pyramidal coordination geometry. Its thermal decomposition procedure detail was studied by thermal analysis TG-DSC. Complex 2 belongs to monoclinic system with space group P2（1）/c and a=0.8897（3） nm, b= 1.9130（8） nm, c= 1.9936（8） nm,β=99.04（2）°, V=3.351（2） nm^3, Z=4, R=0.0540, wR2=0.1102. The structure of 2 is a discrete binucleus, where Cu（1） is four-coordinated by phen and cbdc in a square-planar geometry while Cu（2） is five-coordinated by phen, one O of cbdc and two H2O, which can be best described as distorted trigonal-bipyramidal geometry. Cu（1） and Cu（2） are linked by carboxylic group of cbdc in a bidentate bridging fashion. Variable-temperatttre magnetic susceptibilities of 2 in 2-300 K showed that its magnetic behavior obeyed Curie law.