Flexible and dynamic porous coordination polymers (PCPs) with well-defined nanospaces composed of chromophoric organic linkers provide a scaffold for encapsulation versatile guest molecules through noncovalent interactions. PCPs thus potential platform molecular recognition. Herein, we report flexible 3D supramolecular framework {[Zn(ndc)(o-phen)]⋅DMF}n (o-phen = 1,10-phenanthroline, ndc 2,6-napthalenedicarboxylate) confined that can accommodate different electron-donating aromatic amine...

Abstract In the realm of heterogeneous catalysis, diffusion reactants into catalytically active sites stands as a pivotal determinant influencing both turnover frequency and geometric selectivity in product formation. While accelerated can elevate reaction rates, it often entails compromise selectivity. Porous catalysts, including metal-organic covalent organic frameworks, confront formidable obstacles regulating reactant rates. Consequently, chemical functionality catalysts typically...

Four isostructural chiral three-dimensional (3D) porous pillared-layer frameworks based on Co(II) and Ni(II), {[M(l-mal)(azpy)0.5]·2H2O}n (M = Co (1), Ni (2)) {[M(l-mal)(bpee)0.5]·H2O}n(M (3), (4)); (l-mal l-malate dianion, azpy 4,4′-bisazobipyridine, bpee 1,2-bis(4-pyridyl)ethylene), have been synthesized using mixed ligand systems characterized structurally. All the are homochiral, dianion. The bridging of with or Ni(II) forms a two-dimensional (2D) layer {M(l-mal)}n which is further...

Coordination polymers are well known organic–inorganic hybrids which can be of different dimensionalities; 1D, 2D and 3D. Based on the geometry inorganic metal ions coordination mode organic linkers/clusters extend to dimensions adopt versatile topologies. Frameworks built with one linker or more than (mixed linkers) assembly ions. Use a single is accepted methodology generate high surface area frameworks such as isoreticular metal–organic (IRMOFs), zeolitic imidazolate (ZIFs), HKUST MILs...

The synthesis and adsorption properties of novel, high surface area porous polyimides based on perylene are reported. pore size distribution these polymers were tuned by adopting structure directing trigonal tetrahedral monomers.

We report the synthesis, structural characterization, and porous properties of two isomeric supramolecular complexes ([Cd(NH2 bdc)(bphz)0.5 ]⋅DMF⋅H2 O}n (NH2 bdc=2-aminobenzenedicarboxylic acid, bphz=1,2-bis(4-pyridylmethylene)hydrazine) composed a mixed-ligand system. The first isomer, with paddle-wheel-type Cd2 (COO)4 secondary building unit (SBU), is flexible in nature, whereas other isomer has rigid framework based on μ-oxo-bridged (μ-OCO)2 SBU. Both frameworks are two-fold...

Abstract Functional, porous metal-organic frameworks (MOFs) have attracted much attention as a very flexible class of crystalline, materials. For more advanced applications that exploit photophysical properties, the fabrication hierarchical assemblies, including creation MOF/MOF heterointerfaces, is important. manufacturing superstructures with length scales well beyond MOF pore size, layer-by-layer (lbl) methods are particularly attractive. These allow isoreticular approach to be extended...

A multifunctional porous metal organic framework based on mixed-valence hexa-nuclear [MnIII2MnII4O2(pyz)2(C6H5CH2COO)10] (pyz = pyrazine) units has been synthesized. The complex characterized by elemental analysis, IR spectroscopy, single-crystal X-ray diffraction and variable-temperature magnetic measurements. structural analysis reveals that the bidentate pyz molecules connect each [Mn6] unit to its four neighbors through peripheral Mn(II) centers, giving rise a three-dimensional (3D)...

We herein report an unusual CO2 adsorption behavior in a fluoro-functionalized MOF {[Zn(SiF6)(pyz)2]·2MeOH}n (1) with 1D channel system, which is made up of pyrazine and SiF62− moieties. Surprisingly, desolvated 1 (1′) adsorbs higher amounts at 298 K than 195 K, contrast to the usual trend. Combined Raman spectroscopic theoretical studies reveal that slanted rings 1′ angle 17.2° respect (200) Zn(II)–Si plane low temperature block windows thus reduce uptake amount.

The guest-dependent thermal response of the flexible MOF Zn2(BDC)2(DABCO) (1) has been studied. A series temperature-dependent single crystallographic analyses revealed inherent structural responses 1. guest-free framework 1 exhibited interesting including anisotropic expansion (negative (NTE) along a- and b-axes, positive (PTE) c-axis) disorder-order phase transition. In addition, inclusion guest molecules (DMF benzene) brought distinct to from host-guest interactions. 1·4DMF showed altered...

An ideal material for photon harvesting must allow control of the exciton diffusion length and directionality. This is necessary in order to guide excitons a reaction center, where their energy can drive desired process. To reach this goal both following are required; short- long-range structural detailed understanding excitonic transport. Here we present strategy realize crystalline chromophore assemblies with bespoke architecture. We demonstrate approach by assembling anthracene dibenzoic...

Interpenetration is a natural phenomenon frequently encountered in porous coordination polymers (PCPs) or metal-organic frameworks (MOFs). Traditionally interpenetration has been considered as threat to permanent porosity and several strategies have adopted control the framework interpenetration. Recent literature reports unveiled that paramount importance material properties particularly storage separation of small gas molecules. Such also show interesting structural flexibility based on...

Efficient photon-harvesting materials require easy-to-deposit exhibiting good absorption and excited-state transport properties. We demonstrate an organic thin-film material system, a palladium–porphyrin-based surface-anchored metal–organic framework (SURMOF) thin film that meets these requirements. Systematic investigations using transient spectroscopy confirm triplets are very mobile within single crystalline domains; detailed analysis reveals triplet transfer rate on the order of 1010...

Zirconium-based MOF-on-MOF functional heterostructures achieved by self-assembly of metal node and linker at room temperature.

A three-dimensional (3D) robust porous coordination polymer, {[Cu(azpy)(glut)](H2O)2}n (1) (azpy = N,N′-bis-pyridin-4-ylmethylene-hydrazine, glut glutarate), has been synthesized and structurally characterized. Single crystal X-ray diffraction analysis reveals that each of paddle-wheel Cu2(CO2)4 units is connected with glutarates in the crystallographic bc plane to form a two-dimensional (2D) sheet which pillared by an azpy linker afford 3D framework. Controlled heating as-synthesized 1 at...

Here we report the synthesis and structural characterizations of a new 3D functional metal–organic framework {[K8(PTC)2(H2O)1.5]·4H2O}n formed by self-assembly KI chromophoric linker perylenetetracarboxylate (PTC). The structure determination shows pillared-layer framework, where perylene cores are arranged in an unusual end-to-end off-slipped zigzag arrangement directed KI–carboxylate bonding. Photophysical studies revealed broad absorption band with λmax 531 nm bathochromically shifted red...

In molecular solids, the intense photoluminescence (PL) observed for solvated dye molecules is often suppressed by nonradiative decay processes introduced excitonic coupling to adjacent chromophores. We have developed a strategy avoid this undesirable PL quenching optimizing chromophore packing. integrated photoactive compounds into metal-organic frameworks (MOFs) and tuned alignment introducing adjustable "steric control units" (SCUs). determined optimal of core-substituted...

Abstract Storage and separation of small (C1–C3) hydrocarbons are great significance as these alternative energy resources also can be used raw materials for many industrially important materials. Selective capture greenhouse gas, CO 2 from CH 4 is to improve the quality natural gas. Among available porous materials, MOFs with permanent porosity most suitable serve purposes. Herein, a two‐fold entangled dynamic framework {[Zn (bdc) (bpNDI)]⋅4DMF} n pore surface carved polar functional groups...

Abstract An understanding of solid‐state crystal dynamics or flexibility in metal–organic frameworks (MOFs) showing multiple structural changes is highly demanding for the design materials with potential applications sensing and recognition. However, entangled MOFs such flexible behavior pose a great challenge terms extracting information on their because poor single‐crystallinity. In this article, detailed experimental studies twofold MOF ( f‐MOF‐1) are reported, which unveil its response...

Using pyrene and anthracene monocarboxylate chromophores two metal–organic complexes, {[Cd(pma)2(o-phen)2]·2H2O·MeOH)}n (1) {Cd2(μ-H2O)(amc)4(o-phen)2}n (2) (Hpma = monocarboxylic acid; Hamc 9-anthracene o-phen orthophenanthroline) have been synthesized, respectively characterized using a single crystal X-ray diffraction study. Compound 1 contains seven-coordinated Cd2+ center connected by pma, where one pma pair stacks in face-to-face fashion, the other pma:o-phen is linked through C–H···π...

The light-harvesting properties of two fluorescent dynamic conjugated microporous organic polymers (Py-PP and Py-BPP) rendered with pyrene chromophores are described. hydrophobic nature these porous frameworks allows the selective capture various solvents by instantaneous swelling at room temperature. Moreover, indicates process visible volume expansion enhanced fluorescence. This was further explored for rapid encapsulation chromophoric guests temperature investigated photoinduced energy...

Abstract By using a layer‐by‐layer (LbL) approach, lanthanide‐based, monolithic metal–organic framework (MOF) thin films are fabricated for optical applications. In particular, the LbL approach allows manufacturing of heteroepitaxial Tb(III)‐Eu(III)(BTC) coatings with precise thickness control. Adjusting Tb(III)‐to‐Eu(III) ratio tuning emission color. The hetero‐multilayer architecture makes it possible to suppress direct energy transfer, an unwanted phenomenon present in corresponding...