Host-guest supramolecular interaction behavior at the interface between anode and electrolyte for long life Zn anode

The hydrogen evolution reaction (HER) and dendrite growth associated with Zn anode have become the main bottlenecks for the further development of zinc ion batteries (ZIBs).In this work,the electrochemical activity of H_(3)O^(+) is inhibited by the supramolecular host–guest complex composed of H_(3)O^(+) as guest and 18-crown-6 as host.The even Zn plating is induced by the host–guest complex electrostatic shielding layer on Zn anode,as detected by in-situ optical microscopy.The lamellar Zn is plated which profits from the improved Zn plating behavior.Density functional theory (DFT) calculation presents the stable structure of complex.The less produced H_(2) content is monitored online by a mass spectrometer during Zn plating/stripping,which indicates HER can be hampered by the host–guest behavior.Thus,the ZIBs with long life and high Coulombic efficiency are achieved via introducing 18-crown-6.The proposed host–guest supramolecular interaction is expected to facilitate the furthermore development of Zn batteries.

Tuning host-guest binding model by different intramolecular alkyl chain lengths in tripodal hosts:An evidence on structure control supramolecular interactions

Supramolecular chemistry has received considerable attention in host-guest recognition.The structureresponse relationship of host-guest recognition system is a meaningful issue.Herein,a series of tripodal nitrogen mustard derivatives(TMs)have been developed in this paper.By rationally design the intramolecular alkyl chain lengths of host,the host-guest binding model have been successfully tuned,which underwent a transformation fromπ-πto multiple hydrogen bonds.This process enhances the host-guest binding force and recognition efficiency.

Dopant-free hole transporting materials with supramolecular interactions and reverse diffusion for efficient and modular p-i-n perovskite solar cells

The rational design of dopant-free organic hole-transporting layer(HTL) materials is still a challenge for realizing high-efficient and stable p-i-n planar perovskite solar cells(pero-SCs). Here, we synthesized two π-conjugated small-molecule HTL materials through tailoring the backbone and conjugated side chain to carefully control molecular conformation. The resultant BDT-TPAs Th containing a planar fused benzo[1,2-b:4,5-b′]dithiophene(BDT) core and a conjugated thiophene side chain showed the planar conformation. X-ray crystallography showed a favorable stacking model in solid states under the parallel-displaced π-πand additional S-π weak-bond supramolecular interactions, thus achieving an obviously increased hole mobility without dopants.As an HTL material in p-i-n planar pero-SCs, the marginal solubility of BDT-TPA-s Th enabled inverse diffusion into the perovskite precursor solution for assisting the subsequent perovskite film growth and passivating the uncoordinated Pb2+ ion defects. As a result, the planar p-i-n pero-SCs exhibited a champion power conversion efficiency(PCE) of 20.5% and enhanced moisture stability. Importantly, the BDT-TPA-s Th HTL material also showed weak thickness-photovoltaic dependence, and the pero-SCs with blade-coated BDT-TPA-s Th as a HTL achieved a 15.30% PCE for the 1-cm2 modularized device. This HTL material design strategy is expected to pave the way toward high-performance, dopant-free and printing large-area planar p-i-n pero-SCs.

Proteinaceous Fibers with Outstanding Mechanical Properties Manipulated by Supramolecular Interactions

Proteinaceous fibers based on spidroins have attracted widespread attention due to their lightweight and mechanically strong properties.Presently,mechanical modulation is mainly dependent on the ultrahigh molecular weight of recombinant proteins.This makes it difficult to construct and express the target proteins.It is thus significant to develop alternative strategies for the fabrication of robust biological fibers.Herein,we demonstrate one new type of engineered protein fibers using electrostatic complexation of the cationic elastins and anionic dihydroxyphenylalanine surfactants.Interestingly,the mechanical performance of the resulting fibers can be modulated by multiple supramolecular interactions in the system including electrostatic force,hydrogen bonding,metal coordination,cation-πand other aromatic interactions.Consequently,significant alternation of the fibers’breaking strength(from 32 to 160 MPa),Young’s modulus(from 0.8 to 17 GPa),and toughness(from 1.2 to 99 MJ·m-3)has been achieved.Moreover,the fibers exhibit high plasticity;for example,the formation of different helical structures,and strong fluorescence after the introduction of Tb chelation.Therefore,this study offers new strategies for the mechanical regulation of engineered protein fibers.

Study on the Supramolecular Interaction of β-Cyclodextrin with Gemfibrozil by Spectrofluorimetry and Its Analytical Application

The supramolecular interaction of gemfibrozil with β-cyclodextrin （β-CD） was studied by spectrofluorimetry. The mechanism of the inclusion was discussed by spectrofluoremetry, infrared spectrum and ^1H NMR spectrum. The results showed that a 1 ： 1 （β-CD ： gemfibrozil） complex was formed with an apparent association constant of 3.844 × 10^3 L·mol^-1. Based on the enhancement of the fluorescent intensity of gemfibrozil, a spectrofluorimetric method for the determination of gemfibrozil in bulk aqueous solution in the presence of β-CD was developed. The linear range was 3.30 ng·mL^- 1 -6.00 ug·mL^-1 with the detection limit of 0.980 ng·mL^-1. There was no interference from the excipients normally used in tablet composition and the serum main compositions. The proposed method was then successfully applied to the determination of gemfibrozil in capsules and serum.

Supramolecular interaction controlled and calix[4]arene ligand assisted Pd-catalyzed C(sp3)-H arylation of aliphatic aldehydes

A calix[4]arene ligand assisted directβ-C-H arylation of tertiary aliphatic aldehydes has been developed via a Pd-catalyzed C(sp3)-H functionalization process.This strategy exhibited good functional group compatibility and C-H bond site-selectivity.Mechanism studies have shown that both synergistic effect and cationic-πsupramolecular interaction between calixarene cavity and transition-metal catalytic center may play an important role in this catalytic cycle.This complementary method would be used in organic and medical chemistry due to the importance of tertiary aliphatic aldehydes.

Synthesis and Crystal Structure of a Mixed-ligand Manganese(Ⅱ) Complex Containing Abundant Hydrogen-bonding Interactions

A new mixed-ligand Mn（II）complex,namely [Mn（bipy）2（Huca）]·5H2O（1,bipy = 2,2＇-bipyridine,and H3uca = uracil-5-carboxylic acid）has been prepared and characterized by single-crystal X-ray diffraction,FT-IR spectroscopy and thermogravimetric analysis.It crystallizes in monoclinic,space group C2/c with a = 23.597（8）,b = 16.434（5）,c = 15.531（6）,β = 112.785（6）o,C25H28MnN6O9,Mr = 611.47,V = 5553（3）3,Z = 8,μ = 0.538,Dc = 1.463 g/cm3,F（000）= 2536,R = 0.0441 and wR = 0.1230 for all 5227 observed reflections（I 2σ（I））.The manganese（II）center is surrounded by three bidentate chelating ligands,and it displays a severely distorted octahedral geometry,with cis angles ranging from 72.14（6）to 109.78（6）o.Extensive intermolecular hydrogen bonds link the [Mn（bipy）2（Huca）] monomers and lattice water molecules to yield a three-dimensional supramolecular framework.TGA shows complete removal of all lattice water molecules above 270 ℃.

Syntheses and Structures of Uwo New Oxalate-bridged Transition-metal Supramolecular Polymers of [M(2-NH_2py)_2(ox)]

Two new supramoleeular polymers [ M （2-NH2 py）2 （ox） ] [ M = Co （1）, Ni （2） ; 2-NH2py = 2-aminopyridine; ox = oxalate ] were hydrothermally synthesized and characterized by elemental analyses, IR and single-crystal X-ray diffraction analyses. The isomorphic compounds 1 and 2 both possess one-dimensional zigzag chain structures, which are composed of [ M （2-NH2 py）2 ]^2＋ units bridged by tetradentate oxalate ligands to form three-dimensional supramolecular network v/a the C-H…O hydrogen bonds and π-π stacking interactions. Compound 1 displays antiferromagnetie interaction.

Two Three-dimensional Supramolecular Polymer Built from Mixed N-Donor and Carboxylate Ligands

Two new complexes, [Mn（L）（mmbda）（H_2O）]（1） and [Co（L）（btc）（H_2O）]·H_2O（2）, were synthesized by reacting the corresponding metal（Ⅱ） salts with rigid ligand 1,4-di（1Himidazol-4-yl）benzene（L） and two different carboxylic acids of 5-methylisophthalic acid（H_2mmbda） and 1,2,4-benzenetricarboxylic acid（H_3btc）, respectively. The structures of the complexes were characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in triclinic, space group P1 with a = 6.9436（4）, b = 9.7306（6）, c = 15.5302（10） ？, α = 73.7430（10）, β = 85.1010（10）, γ = 70.0360（10）o, V = 946.75（10） ？~3, Z = 2, C_（21）H_（20）N_4O_5 Mn, M_r = 463.33, D_c = 1.618 g/cm^3, μ = 0.742-1, S = 1.002, F（000） = 474, the final R = 0.0285 and wR = 0.0600 for 4328 observed reflections（I 〉 2σ（I））. Complex 2 crystallizes in monoclinic, space group P2_1/n with a = 12.5216（12）, b = 7.3312（8）, c = 22.510（2） ？, β = 93.104（2）o, V = 2063.3（4） ？~3, Z = 4, C_（21）H_（18）N_4O_8Co, M_r = 513.31, D_c = 1.646 g/cm^3, μ = 0.892^（-1） mm, S = 1.096, F（000） = 1044, the final R = 0.0673 and wR = 0.1780 for 3594 observed reflections（I 〉 2σ（I））. Both of complexes are one-dimensional（1D） chain structures and rich hydrogen bonds extend such 1D chains to form three-dimensional（3D） supramolecular polymers.

In situ crosslink polymerization induced long-lived multicolor supramolecular hydrogel based on modifiedβ-cyclodextrin

The construction of hydrogels with good mechanical properties and phosphorescent properties is full of challenges.Herein,we report a supramolecular phosphorescent hydrogel with long lifetime,high tensile strength and self-healing property,which can be easily constructed through in-situ thermalinitiated polymerization of isocyanatoethyl acrylate-modifiedβ-cyclodextrin(β-CD-DA)and acrylatemodified adamantane(Ad-DA),acrylic acid(AA),followed by the non-covalent association with carbon dots(CNDs).The lifetime of phosphorescent hydrogel can reach 1261 ms at room temperature,and the quantum yield is 11%.Importantly,through the efficient triplet to singlet Förster resonance energy transfer(TS-FRET),the phosphorescent hydrogel shows the good phosphorescence energy transfer property for organic dyes Rhodamine B and Eosin Y with the delayed fluorescence lifetime up to 730 ms and 585 ms as well as the energy transfer efficiency(Φ_(ET))up to 99.9%and 99.3%,respectively.Moreover,owing to the host-guest interactions betweenβ-CD-DA and Ad-DA,the three-dimensional cross-linked network phosphorescent hydrogel can be easily stretched to 18 times of its original length,and can achieve self-healing of the cut surfaces within 30 min.These results will expand the scope of phosphorescent materials and provide new ideas and opportunities for materials science.

Supramolecular Bonding Competition Enabled Nanostructure Evolution and Mechanical Reinforcement

In this work,competition between different supramolecular interactions is investigated based on a fibrous crystal composed of hydrogen-bonded cyanuric acid(CA)and amidinothiourea(ADT).Melamine(M)is found to prevail over ADT and bond to CA due to its stronger triple H-bonding affiliation,forming hollow microtubes assembled by oriented CAM crystalline arrays,as guided by the directionality of peripheral hydrogen bonds.Furthermore,competitive interaction between hydrogen bonding and ionic/covalent bonding is demonstrated by mixing Ag+ions with the CA-ADT fibers,where sulfur atoms are abstracted from ADT molecules to produce Ag_(2)S ligaments.The in situ-formed Ag_(2)S serves as a binding glue to generate CA-ADT/Ag_(2)S composites with significantly enhanced mechanical strength compared to the pristine CA-ADT fiber pellet.

Two Zinc Architectures:A Mononuclear Complex and a 2D Wave-like Organic-inorganic Hybrid Layer

Self-assembly of Zn（NO3）2·6H2O and 2,3,5,6-tetrabromoterephthalic acid（H2TBTA） gave rise to two new zinc metal-organic frameworks,Zn（HTBTA）2（phen）2·H2O（1） and Zn（TBTA）1/2（μ2-OH）（H2O）·0.25EtOH（2）.Complex 1 is a mononuclear molecule.The hydrogen bonding interactions further connect the mononuclear molecules to generate a 2D supramolecular architecture.Complex 2 is a 2D organic-inorganic hybrid layer framework constructed from 1D rod-shaped secondary building units.

Synthesis, Crystal Structure and Luminescent Property of [Zn(C_(12)H_9O_3)_2(C_(10)H_8N_2)]_n·nH_2O

Under hydrothermal condition, the reaction of 2-naphthoxyacetic acid with ZnCl2 and 4,4′-bipyridine （4,4′-bipy） has afforded a new Zn（Ⅱ） compound, [Zn（C12H9O3）2（C10H8N2）]n·nH2O1, which was structurally characterized by single-crystal X-ray diffraction analysis. The crystal is of monoclinic, space group P21/c with a = 7.7335（2）, b = 19.3834（4）, c = 20.1707（4） A, β = 104.9830（10）°, V = 2920.82（11） A^3, C34H28ZnN2O7, Mr = 641.95, Z = 4, Dc = 1.460 g/cm^3,μ = 0.895 mm^-1, F（000） = 1328, R = 0.0406 and wR = 0.0876 for 4417 observed reflections （I〉 2σ（I）） Complex 1 consists of one-dimensional zigzag chains deriving from Zn（C12H9O3）2 units linked by 4,4′-bipy ligands, and lattice water molecules decorate between the chains. Non-covalent interactions, such as hydrogen-bonding and aromatic π-π interactions, lead to the formation of a 3D network structure. The thermogravimetric analysis （TGA） and luminescent property for 1 have also been studied in this paper.

Effect of Calix[4]pyrrole as Addition Reagent on Anions Separation in Capillary Zone Electrophoresis (CZE)

Supramolecular interaction of calix[4]pyrroles with several inorganic anions is reported by addition of calix[4]pyrroles to background electrolyte (BGE) in CZE. The retention time (t(R)) of all anions increased with increasing concentration of calix[4]pyrroles. The effect on F- is most evident.

Sensitized effect of β-cyclodextrin on the fluorescence in the determination of carbaryl

Based on the significant enhancement of fluorescence intensity of carbaryl in inclusion complex, a spetrofluorimetric method with high sensitivity was developed for the determination of carbaryl in aqueous solution. Under the optimum conditions, the complex had excitation and emission maxima at 278 nm and 332 nm, respectively. The linear range of the method was 7.0 ng/ml—1500 ng/ml with a detection limit of 1.2 ng/ml. The proposed method was successfully used to determine quantitatively of carbaryl in cottonseeds.

Crossed Ladders in a 2-D Mixed-ligand Lanthanide Coordination Polymer:Synthesis,Crystal Structure and Photoluminescence

A new metal-organic coordination polymer, [Ce（L1）（L2）（H2O）]2H2O （1, H2L1 = 2,6-dimethylpyridine-3,5-diearboxylie acid, H2L2 = （E）-2,6-dimethyl-4-styrylpyridine-3,5-dieerboxylie acid）, has been synthesized and characterized by elemental analysis, IR, and X-ray single-crystal diffraction. Compound 1 crystallizes in trielinic, space group P1 and displays a two-dimensional coordination network structure. In 1, the relatively rare crossed ladders constructed by mixed ligands organize a 2-D grid with the topology of （426）2（48668）, and the layers further build up a 3-D supramoleeular architeetttre via interlaminar hydrogen bonds.

Syntheses,Crystal Structures and Catalytic Properties of Copper(Ⅱ) and Cobalt(Ⅱ) Complexes Containing 5,6-Dimethylbenzimidazole

Two new complexes, [Cu（DMB）2（NAA）2]（1） and [Co（DMB）2（NAA）2]（2）（DMB = 5,6-dimethylbenzimidazole, HNNA = 1-naphthylacetic acid）, were hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, TGA, PXRD and single-crystal X-ray diffraction analysis. The coordination geometry of the metal centers is a perfect square plane for 1 and a distorted tetrahedron for 2. In compound 1, the mononuclear units are linked by N–H···O hydrogen bonds to form a 1D chain structure, while mononuclear motifs of 2 are extended via N–H···O hydrogen bonding and π-π stacking interactions into a 2D supramolecular layer. The remarkable catalytic properties of the two complexes for the degradation of Congo red dye have been found.

Synthesis and Characterization of a Manganese(Ⅱ) Coordination Compound with Two-dimensional Layer Structure: {[Mn_2(IP)_2(1,4-bdc)_2]·H_2O}n

A new complex {[Mn2（IP）2（1,4-bdc）2]·H2O}n（1）（IP = 1H-imidazo[4,5-f][1,10]-phenanthroline, 1,4-H2 bdc = 1,4-benzendicarboxylic acid）, have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group Cc with a = 20.326（2）, b = 24.249（2）, c = 7.621（1）A, β = 108.546（6）, V = 3561.2（7）A3, Z = 4, Dc = 1.672 g/cm^3, μ = 0.785 mm^-1, F（000） = 1824, S = 1.067, the final R = 0.0299 and wR = 0.0752. Compound 1 possesses a 2D structural motif, in which two crystallographically independent 1,4-bdc dianions adopt the alternative mode of mixed bis（bidentate） and monodentate-bidentate coordination modes to bridge neighboring Mn（II） centers. And the 2D layers are linked up by hydrogen bonding and π···π stacking interactions to form a 3D network. The title compound has good thermal stability and exhibits photoluminescent emission maximum at 518 nm.

Thermodynamics of the long range assembly of safranine T on molecular surfaces of nucleic acids

By making use of the fluorescence quenching properties of safranine T(ST) in its long range assembly on the molecular surfaces of nucleic acids, the assembly number and constant of ST with calf thymus DNA, fish sperm DNA and yeast RNA were determined at 12℃. The corresponding free energy change, enthalpy change and entropy change of the long range assembly were calculated at the same temperature. It was found the assembly complexes are very stable and the assembly is a spontaneous process characterized an entropy increase.

A supramolecular bottlebrush polymer assembled on the basis of cucurbit[8]uril-encapsulation-enhanced donor-acceptor interaction

A supramolecular bottlebrush polymer has been constructed in water through the self-assembly of a rigid electron-deficient building block and an electron-rich monomer which bears two tetraethylene glycol chains,driven by CB[8]-encapsulation-enhanced donor-acceptor interaction.The as-formed supramolecular bottlebrush polymer has been characterized by -1H NMR titration experiment,UV-vis spectroscopy,DLS and 2D -1H NMR DOSY.