Structural‐Deformation‐Energy‐Modulation Strategy in a Soft Porous Coordination Polymer with an Interpenetrated Framework

To achieve unique molecular‐recognition patterns, a rational control of the flexibility of porous coordination polymers (PCPs) is highly sought, but it remains elusive. From a thermodynamic perspective, the competitive relationship between the structural deformation energy (E_def) of soft PCPs and the guest interaction is key for selective a guest‐triggered structural‐transformation behavior. Therefore, it is vital to investigate and control E_def to regulate this competition for flexibility control. Driven by these theoretical insights, we demonstrate an E_def‐modulation strategy via encoding inter‐framework hydrogen bonds into a soft PCP with an interpenetrated structure. As a proof of this concept, the enhanced E_def of PCP enables a selective gate‐opening behavior toward CHCl₃ over CH₂Cl₂ by changing the adsorption‐energy landscape of the compounds. This study provides a new direction for the design of functional soft porous materials.     

含有微孔结构的吡啶二羧酸金属锰配位聚合物(英文)

<正>0 Introduction The realm of crystal engineering has provided a sound junction between aesthetics of crystalline architectures[1-2]and their potential functions[3-4],of which the ultimate destination is to successfully achieve     

Recognition of 1,3‐Butadiene by a Porous Coordination Polymer

The separation of 1,3‐butadiene from C₄ hydrocarbon mixtures is imperative for the production of synthetic rubbers, and there is a need for a more economical separation method, such as a pressure swing adsorption process. With regard to adsorbents that enable C₄ gas separation, [Zn(NO₂ip)(dpe)]_n (SD‐65; NO₂ip=5‐nitroisophthalate, dpe=1,2‐di(4‐pyridyl)ethylene) is a promising porous material because of its structural flexibility and restricted voids, which provide unique guest‐responsive accommodation. The 1,3‐butadiene‐selective sorption profile of SD‐65 was elucidated by adsorption isotherms, in situ PXRD, and SSNMR studies and was further investigated by multigas separation and adsorption–desorption‐cycle experiments for its application to separation technology.     

Storage of CO2 into Porous Coordination Polymer Controlled by Molecular Rotor Dynamics

Design to store gas molecules, such as CO₂, H₂, and CH₄, under low pressure is one of the most important challenges in chemistry and materials science. Herein, we describe the storage of CO₂ in the cavities of a porous coordination polymer (PCP) using molecular rotor dynamics. Owing to the narrow pore windows of PCP, CO₂ was not adsorbed at 195 K. As the temperature increased, the rotors exhibited rotational modes; such rotations dynamically expanded the size of the windows, leading to CO₂ adsorption. The rotational frequencies of the rotors (k≈10^?6 s) and correlation times of adsorbed CO₂ (τ≈10^?8 s) were elucidated via solid‐state NMR studies, which suggest that the slow rotation of the rotors sterically restricts CO₂ diffusion in the pores. This restriction results in an unusually slow CO₂ mobility close to solid state (τ≥10^?8 s). Once adsorbed at room temperature, CO₂ is robustly stored in the PCP under vacuum at 195–233 K because of the steric hindrance of the rotors. We also demonstrate that this mechanism can be applied to the storage of CH₄.     

Formation of Foam‐like Microstructural Carbon Material by Carbonization of Porous Coordination Polymers through a Ligand‐Assisted Foaming Process

Porous carbon material with a foam‐like microstructure has been synthesized by direct carbonization of porous coordination polymer (PCP). In situ generation of foaming agents by chemical reactions of ligands in PCP during carbonization provides a simple way to create lightweight carbon material with a foam‐like microstructure. Among several substituents investigated, the nitro group has been shown to be the key to obtain the unique foam‐like microstructure, which is due to the fast kinetics of gas evolution during carbonization. Foam‐like microstructural carbon materials showed higher pore volume and specific capacitance compared to a microporous carbon.     

Amine‐Responsive Adaptable Nanospaces: Fluorescent Porous Coordination Polymer for Molecular Recognition

Flexible and dynamic porous coordination polymers (PCPs) with well‐defined nanospaces composed of chromophoric organic linkers provide a scaffold for encapsulation of versatile guest molecules through noncovalent interactions. PCPs thus provide a potential platform for molecular recognition. Herein, we report a flexible 3D supramolecular framework {[Zn(ndc)(o‐phen)]?DMF}_n (o‐phen=1,10‐phenanthroline, ndc=2,6‐napthalenedicarboxylate) with confined nanospaces that can accommodate different electron‐donating aromatic amine guests with selective turn‐on emission signaling. This system serves as a molecular recognition platform through an emission‐readout process. Such unprecedented tunable emission with different amines is attributed to its emissive charge‐transfer (CT) complexation with o‐phen linkers. In certain cases this CT emission is further amplified by energy transfer from the chromophoric linker unit ndc, as evidenced by single‐crystal X‐ray structural characterization.     

A Highly Connected Porous Coordination Polymer with Unusual Channel Structure and Sorption Properties

Making connections : A hydroxy‐centered trinuclear nickel cluster has been employed to construct a highly connected, highly symmetric framework with a uninodal nine‐connected topology. An array of triakis tetrahedra leads to a biporous intersecting‐channel system (see picture).

     

A Dual‐Ligand Porous Coordination Polymer Chemiresistor with Modulated Conductivity and Porosity

Single‐ligand‐based electronically conductive porous coordination polymers/metal–organic frameworks (EC‐PCPs/MOFs) fail to meet the requirements of numerous electronic applications owing to their limited tunability in terms of both conductivity and topology. In this study, a new 2D π‐conjugated EC‐MOF containing copper units with mixed trigonal ligands was developed: Cu₃(HHTP)(THQ) (HHTP=2,3,6,7,10,11‐hexahydrotriphenylene, THQ=tetrahydroxy‐1,4‐quinone). The modulated conductivity (σ≈2.53×10^?5 S cm^?1 with an activation energy of 0.30 eV) and high porosity (ca. 441.2 m² g^?1) of the Cu₃(HHTP)(THQ) semiconductive nanowires provided an appropriate resistance baseline and highly accessible areas for the development of an excellent chemiresistive gas sensor.     

Ytterbium Coordination Polymer with Four Different Coordination Numbers：The First Structural Characterization of Lanthanide Phthalate Complex

The novel ytterbium coordination polymer is a t4wo-dimensional framework in which the central metal ions have four different coordination numbers and form four kinds of coordination poly-hedra,The four kinds of coordination polyhedra connect into infinite chains by sharing oxygen atoms.     

Luminescent Copper(I)-Complexes with an Anionic NHC obtained via a Coordination Polymer as Versatile Precursor**

The anionic diamido N-heterocyclic carbene 1 is used to prepare a series of linear as well as trigonal, heteroleptic Cu^I complexes with small molecular ligands such as pyridine derivatives or triphenylphosphine. A key role lies in the versatile precursor for these complexes, a moisture- and air-stable 1D coordination polymer [1 ⋅ Cu] _n composed of only the NHC ligand and Cu^I, such that the copper is linearly coordinated by the carbene carbon atom and one oxygen atom of the backbone of the carbene. This polymer can easily be cleaved into monomeric complexes by addition of the desired ligand to dispersions of the polymer in dichloromethane. In solution, the complexes are in equilibrium with this highly insoluble polymer and free ligand. Thus, analytical and spectroscopical experiments with the compounds are limited to their crystalline state, characterized by single crystal X-ray diffraction experiments. Some of the complexes exhibit visible luminescence in the solid state upon irradiation with ultraviolet light. The spectral features (emission wavelength, Stokes shift, width of the emission band, vibrational fine structure) significantly differ among the complexes. Quantum mechanical computations reveal a subtle interplay of several factors such as coordination number and charge transfer character of the emissive state.     

A Porous Coordination Polymer with Accessible Metal Sites and its Complementary Coordination Action

Broken switch : Guest‐accessible metal sites are generated on the pore surface of a porous coordination polymer (see figure) through the complementary coordination‐bond rearrangement in a single‐crystal‐to‐single‐crystal fashion, which is triggered by the removal of coordinated water.

     

Synthesis,Crystal Structure,and Magnetic Properties of a New 2D Twofold Interpenetrated Coordination Polymer [Cu(3,4‐pybz)2]n

A new coordination polymer, [Cu(3, 4‐pybz)₂]_n ( 1 ) [3,4‐Hpybz = 3‐pyridin‐4‐yl‐benzoic acid], was synthesized by hydrothermal reaction of CuCl₂ · 2H₂O and 3,4‐Hpybz, and characterized by elemental analysis, IR spectroscopy, PXRD, and single‐crystal X‐ray diffraction. The structure determination reveals that 1 exhibits a 2D twofold interpenetrated 4‐connected (4,4) network topology, these 2D layers are further enlarged to form the final 3D supramolecular edifice via aromatic π–π stacking interactions. In addition, the magnetic behavior and thermogravimetric analysis of 1 were also studied.     

Two-Dimensional (2D) Porous Zinc Oxides Derived from the Coordination Polymer via Chemical-Assisted Phase Transition

Two-dimensional (2D) porous zinc oxides (ZnO) were successfully prepared via chemical treatment and thermal annealing of coordination polymers (CPs) precursors consisting of Zn(II) ion and fumarate ligand. The morphology, crystalline phase, chemical state, and surface area of the resultant ZnO were characterized. It is experimentally discovered that the crystal phase of the CP bearing Zn(II) ions is transformed to the zinc hydroxide crystal phase by chemical treatment using ammonia water. The prepared CP-derived porous 2D ZnO exhibited enhanced photocatalytic efficiency for dye degradation under black-light irradiation (365 nm) compared to CP-derived non-porous ZnO without a chemical-assisted phase transition process.     

Synthesis and Structure of a Cerium Coordination Polymer Templated by Double-Keggin-anion

A porous coordination polymer, {[Ce（dpdo）4（H2O）3]（PMo_12O_40）（dpdo）0.5（H2O）4}n 1 （dpdo = 4,4＇-bipyridine-N,N＇-dioxide）, templated by double-Keggin-type polyanions was synthesized and structurally characterized. The crystal structure was determined by single-crystal X- ray diffraction. The crystal is of triclinic, space group P1 with a = 13.368（4）, b = 16.503（4）, c = 18.506（5）А, α = 88.831（5）, β= 82.095（5）, γ = 83.578（5）°,V= 4018.6（18）А^3, Z=2, C45H50N9O56CeMo12P, Mr = 2935.31, Dc = 2.426 g/m^3, μ= 2.491 mm^-1, F（000） = 2816, the final R=0.0603 and wR = 0.1611 for 11977 observed reflections with I 〉 2σ（I）. Compound 1 exhibits a 3D non-interwoven framework with large cavities housing centrosymmetrically related shoulder-by-shoulder double-Keggin anions as guests.     

Enhanced Phosphorescence Emission by Incorporating Aromatic Halides into an Entangled Coordination Framework Based on Naphthalenediimide

Phosphorescence emission at room temperature is turned on in an entangled porous coordination polymer (PCP) with naphthalenediimide (NDI) as chromophore, by incorporating halogenated guests into the pores. The phosphorescent efficiency is drastically increased by the incorporation of aromatic halide guests in comparison with the incorporation of nonaromatic derivatives. Aromatic halide guests trigger a structural transformation, which allows a strong interaction with the NDI ligand in the framework through charge‐transfer complexation, and provides an extra population process of the triplet state. The long‐lived photoinduced triplet states, with an emission wavelength in the red region of the visible spectrum, demonstrated by this PCP, may open the door for potential uses, for example, as singlet‐oxygen generators or for bio‐imaging applications.     

A Novel Borophosphate Coordination Polymer with Sandwich-type Supramolecular Architecture

A novel borophosphate (Hmel)3{Co2[(mel)2(HPO4)2(PO4)]·H3BO3·H2O} (mel= melamine) has been synthesized under mild solvothermal conditions. The structure of the compound exists a high ordered organic-inorganic sandwich-type supramolecular architecture via metal-coordination, hydrogen bonds and π-π stacking interactions.     

Arene Selectivity by a Flexible Coordination Polymer Host

The coordination polymers [Ag₄(O₂CCF₃)₄(phen)₃] ? phen ? arene ( 1? phen ? arene) (phen=phenazine; arene=toluene, p‐xylene or benzene) have been synthesised from the solution phase in a series of arene solvents and crystallographically characterised. By contrast, analogous syntheses from o‐xylene and m‐xylene as the solvent yield the solvent‐free coordination polymer [Ag₄(O₂CCF₃)₄(phen)₂] ( 2 ). Toluene, p‐xylene and benzene have been successfully used in mixed‐arene syntheses to template the formation of coordination polymers 1? phen ? arene, which incorporate o‐ or m‐xylene. The selectivity of 1? phen ? arene for the arene guests was determined, through pairwise competition experiments, to be p‐xylene>toluene≈benzene>o‐xylene>m‐xylene. The largest selectivity coefficient was determined as 14.2 for p‐xylene:m‐xylene and the smallest was 1.0 for toluene:benzene.     

抗菌药物柳氮磺胺镉配聚物的合成和晶体结构

0 Introduction Crystal engineering of pharmaceutical solids rep- resents a fertile and emerging research filed[1]. The im- petus for discovery of diverse crystal forms of drugs stems from the critical need to balance stability, bioavailability and other performance characteristics as well as provides valuable intellectual property pro- tection. Sulfasalazine (synonyms salazopyridine and salazosulfapyridine, abbreviated as H-SSZ) is a conju- gate of 5-aminosalicylic acid and sulfapyridine pos…     

三维开放骨架镧系金属有机配位聚合物Tm(BTC)(DMF)(DMSO)的合成、结构和性质

以稀土元素铥(Tm) 作为金属中心, 均苯三甲酸(H3BTC)作为有机配体制备了一个新型的三维配位聚合物 Tm(BTC)(DMF)(DMSO), 并通过X射线单晶衍射、元素分析、热重分析、吸附测试等手段对其进行了表征.