Modulating Photo- and Radioluminescence in Tb(III) Cluster-Based Metal–Organic Frameworks

X Ray ◽

Metal Organic ◽

Facile Route

Luminescent metal–organic frameworks (MOFs) are of interest for sensing, theranostics, dosimetry, and other applications. The use of lanthanoids in MOF metal nodes allows for intrinsic met-al-based luminescence. In this work, a facile route for modulat-ing the photoluminescent and radioluminescent properties of Tb(III)-based MOFs is reported. By using Tb(III)-cluster nodes as X-ray attenuators, and organic linkers with varying excited state energies as sensitizers, MOFs with metal-based, linker-based, and metal+linker-based photo- and radioluminescence are reported.

Synthesis, crystal structure, luminescence, and photocatalytic properties of a 2D Cu(II) metal-organic frameworks based on 3,5-di(1H-benzimidazol-1-yl)pyridine and 4,4′-oxybis(benzoate) ligands

Zeitschrift für Naturforschung B ◽

10.1515/znb-2020-0041 ◽

2020 ◽

Vol 75 (8) ◽

pp. 727-732

Author(s):

Chen Zhang ◽

Jian-Qing Tao

Keyword(s):

Crystal Structure ◽

Thermal Analysis ◽

Uv Light ◽

Metal Organic Framework ◽

X Ray Diffraction ◽

X Ray ◽

Uv Light Irradiation ◽

Photocatalytic Activities ◽

AbstractA new Cu(II) metal-organic framework, [Cu(L)(OBA)·H2O]n (1) [H2OBA = 4,4′-oxybis(benzoic acid), L = 3,5-di(1H-benzimidazol-1-yl)pyridine] was hydrothermally synthesized and characterized through IR spectroscopy, elemental and thermal analysis and single-crystal X-ray diffraction. Complex 1 is a four-connected uni-nodal 2D net with a (44·62) topology which shows an emission centered at λ ∼393 nm upon excitation at λ = 245 nm. Moreover, complex 1 possesses high photocatalytic activities for the decomposition of Rhodamine B (RhB) under UV light irradiation.

In situ X‐ray Diffraction Investigation of the Crystallisation of Perfluorinated Ce(IV)‐based Metal‐Organic Frameworks with UiO‐66 and MIL‐140 architectures

Chemistry - A European Journal ◽

10.1002/chem.202005085 ◽

2021 ◽

Author(s):

Stephen J. I. Shearan ◽

Jannick Jacobsen ◽

Ferdinando Costantino ◽

Roberto D’Amato ◽

Dmitri Novikov ◽

...

Keyword(s):

X Ray Diffraction ◽

X Ray ◽

A series of microporous and robust Ln-MOFs showing luminescent properties and catalytic performances towards Knoevenagel reactions

Dalton Transactions ◽

10.1039/d1dt03188k ◽

2021 ◽

Author(s):

Qing-Xia Yao ◽

Miaomiao Tian ◽

Jun Zheng ◽

Jintang Xue ◽

Xuze Pan ◽

...

Keyword(s):

Single Crystal ◽

Luminescent Properties ◽

X Ray Diffraction ◽

X Ray ◽

Metal Organic ◽

Catalytic Performances

A series of microporous Ln(III)-based metal-organic frameworks (1-Ln) have been hydrothermally synthesized by using 4,4',4''-nitrilotribenzoic acid (H3NTB). Single crystal X-ray diffraction analyses show 1-Ln are isostructural and have 3D porous...

Compressibility Studies of Zirconium Based Metal-Organic Frameworks

Acta Crystallographica Section A Foundations and Advances ◽

10.1107/s2053273314098428 ◽

2014 ◽

Vol 70 (a1) ◽

pp. C157-C157

Author(s):

Claire Hobday ◽

Stephen Moggach ◽

Carole Morrison ◽

Tina Duren ◽

Ross Forgan

Keyword(s):

High Pressure ◽

Mechanical Stability ◽

External Pressure ◽

X Ray Diffraction ◽

X Ray ◽

X Ray Crystallography ◽

Pressure Medium ◽

Metal Organic ◽

University Of Oslo

Metal-organic frameworks (MOFs) are a well-studied class of porous materials with the potential to be used in many applications such as gas storage and catalysis.[1] UiO-67 (UiO = University of Oslo), a MOF built from zirconium oxide units connected with 4,4-biphenyldicarboxylate (BDC) linkers, forms a face centred cubic structure. Zirconium has a high affinity towards oxygen ligands making these bridges very strong, resulting in UiO-based MOFs having high chemical and thermal stability compared to other MOF structures. Moreover, UiO-67 has become popular in engineering studies due to its high mechanical stability.[2] Using high pressure x-ray crystallography we can exert MOFs to GPa pressures, experimentally exploring the mechanical stability of MOFs to external pressure. By immersing the crystal in a hydrostatic medium, pressure is applied evenly to the crystal. On surrounding a porous MOF with a hydrostatic medium composed of small molecules (e.g. methanol), the medium can penetrate the MOF, resulting in medium-dependant compression. On compressing MOF-5 (Zn4O(BDC)3) using diethylformamide as a penetrating medium, the framework was shown to have an increased resistance to compression, becoming amorphous several orders of magnitude higher in pressure than observed on grinding the sample.[3] Here we present a high-pressure x-ray diffraction study on the UiO-based MOF UiO-67, and several new synthesised derivatives built from same metal node but with altered organic linkers, allowing us to study in a systematic way, the mechanical stability of the MOF, and its pressure dependence on both the linker, and pressure medium.

Four Novel d10 Metal-Organic Frameworks Incorporating Amino-Functionalized Carboxylate Ligands: Synthesis, Structures, and Fluorescence Properties

Frontiers in Chemistry ◽

10.3389/fchem.2021.708314 ◽

2021 ◽

Vol 9 ◽

Author(s):

Wang Xie ◽

Jie Wu ◽

Xiaochun Hang ◽

Honghai Zhang ◽

Kang shen ◽

...

Keyword(s):

Three Dimensional ◽

Fluorescence Properties ◽

Gravimetric Analysis ◽

X Ray Diffraction ◽

X Ray ◽

Quenching Effect ◽

D10 Metal ◽

Metal Organic ◽

Point Symbol

By employment of amino-functionalized dicarboxylate ligands to react with d10 metal ions, four novel metal-organic frameworks (MOFs) were obtained with the formula of {[Cd(BCPAB)(μ2-H2O)]}n (1), {[Cd(BDAB)]∙2H2O∙DMF}n (2), {[Zn(BDAB)(BPD)0.5(H2O)]∙2H2O}n (3) and {[Zn(BDAB)(DBPB)0.5(H2O)]∙2H2O}n (4) (H2BCPAB = 2,5-bis(p-carbonylphenyl)-1-aminobenzene; H2BDAB = 1,2-diamino-3,6-bis(4-carboxyphenyl)benzene); BPD = (4,4′-bipyridine); DBPB = (E,E-2,5-dimethoxy-1,4-bis-[2-pyridin-vinyl]-benzene; DMF = N,N-dimethylformamide). Complex 1 is a three-dimensional (3D) framework bearing seh-3,5-Pbca nets with point symbol of {4.62}{4.67.82}. Complex 2 exhibits a 4,4-connected new topology that has never been reported before with point symbol of {42.84}. Complex 3 and 4 are quite similar in structure and both have 3D supramolecular frameworks formed by 6-fold and 8-fold interpenetrated 2D coordination layers. The structures of these complexes were characterized by single crystal X-ray diffraction (SC-XRD), thermal gravimetric analysis (TGA) and powder X-ray diffraction (PXRD) measurements. In addition, the fluorescence properties and the sensing capability of 2–4 were investigated as well and the results indicated that complex 2 could function as sensor for Cu2+ and complex 3 could detect Cu2+ and Ag+via quenching effect.

In situ X-ray Diffraction Investigation of the Crystallisation of Perfluorinated Ce(IV)-based Metal-Organic Frameworks with UiO-66 and MIL-140 architectures

10.26434/chemrxiv.13252544 ◽

2020 ◽

Author(s):

Stephen Shearan ◽

Jannick Jacobsen ◽

Ferdinando Costantino ◽

Roberto D’Amato ◽

Dmitri Novikov ◽

...

Keyword(s):

Crystal Growth ◽

Building Blocks ◽

Nucleation And Growth ◽

X Ray Diffraction ◽

X Ray ◽

Rate Determining Step ◽

Wide Range ◽

We report on the results of a thorough in situ synchrotron powder X-ray diffraction study of the crystallisation in aqueous medium of two recently discovered perfluorinated Ce(IV)-based metal-organic frameworks (MOFs), analogues of the already well investigated Zr(IV)-based UiO-66 and MIL-140A, namely, F4_UiO-66(Ce) and F4_MIL-140A(Ce). The two MOFs were originally obtained in pure form in similar conditions, using ammonium cerium nitrate and tetrafluoroterephthalic acid as building blocks, and small variations of the reaction parameters were found to yield mixed phases. Here, we investigate the crystallisation of these compounds in situ in a wide range of conditions, varying parameters such as temperature, amount of the protonation modulator nitric acid (HNO3) and amount of the coordination modulator acetic acid (AcOH). When only HNO3 is present in the reaction environment, F4_MIL-140A(Ce) is obtained as a pure phase. Heating preferentially accelerates nucleation, which becomes rate determining below 57 °C, whereas the modulator influences nucleation and crystal growth to a similar extent. Upon addition of AcOH to the system, alongside HNO3, mixed-phased products, consisting of F4_MIL-140A(Ce) and F4_UiO-66(Ce), are obtained. In these conditions, F4_UiO-66(Ce) is always formed faster and no interconversion between the two phases occurs. In the case of F4_UiO-66(Ce), crystal growth is always the rate determining step. An increase in the amount of HNO3 slows down both nucleation and growth rates for F4_MIL-140A(Ce), whereas nucleation is mainly affected for F4_UiO-66(Ce). In addition, a higher amount HNO3 favours the formation of F4_MIL-140A(Ce). Similarly, increasing the amount of AcOH leads to slowing down of the nucleation and growth rate, but favours the formation of F4_UiO-66(Ce). The pure F4_UiO-66(Ce) phase could also be obtained when using larger amounts of AcOH in the presence of minimal HNO3. Based on these in situ results, a new optimised route to achieving a pure, high quality F4_MIL-140A(Ce) phase in mild conditions (60 °C, 1 h) is also identified.

Philosophical Transactions of The Royal Society A Mathematical Physical and Engineering Sciences ◽

X-ray crystallographic insights into post-synthetic metalation products in a metal–organic framework

10.1098/rsta.2016.0028 ◽

2017 ◽

Vol 375 (2084) ◽

pp. 20160028 ◽

Cited By ~ 11

Author(s):

Michael T. Huxley ◽

Campbell J. Coghlan ◽

Witold M. Bloch ◽

Alexandre Burgun ◽

Christian J. Doonan ◽

...

Keyword(s):

Transition Metal ◽

Metal Complexes ◽

Transition Metal Complexes ◽

Coordination Sphere ◽

Void Space ◽

X Ray ◽

X Ray Crystallography ◽

Metal Nitrates ◽

Post-synthetic modification of metal–organic frameworks (MOFs) facilitates a strategic transformation of potentially inert frameworks into functionalized materials, tailoring them for specific applications. In particular, the post-synthetic incorporation of transition-metal complexes within MOFs, a process known as ‘metalation’, is a particularly promising avenue towards functionalizing MOFs. Herein, we describe the post-synthetic metalation of a microporous MOF with various transition-metal nitrates. The parent framework, 1 , contains free-nitrogen donor chelation sites, which readily coordinate metal complexes in a single-crystal to single-crystal transformation which, remarkably, can be readily monitored by X-ray crystallography. The presence of an open void surrounding the chelation site in 1 prompted us to investigate the effect of the MOF pore environment on included metal complexes, particularly examining whether void space would induce changes in the coordination sphere of chelated complexes reminiscent of those found in the solution state. To test this hypothesis, we systematically metalated 1 with first-row transition-metal nitrates and elucidated the coordination environment of the respective transition-metal complexes using X-ray crystallography. Comparison of the coordination sphere parameters of coordinated transition-metal complexes in 1 against equivalent solid- and solution-state species suggests that the void space in 1 does not markedly influence the coordination sphere of chelated species but we show notably different post-synthetic metalation outcomes when different solvents are used. This article is part of the themed issue ‘Coordination polymers and metal–organic frameworks: materials by design’.

Cu-based metal-organic frameworks for highly sensitive X‑ray detector

Chemical Communications ◽

10.1039/d1cc03458h ◽

2021 ◽

Author(s):

Zheng Li ◽

Shuquan Chang ◽

Haiqian Zhang ◽

Yong Hu ◽

Yulong Huang ◽

...

Keyword(s):

Activation Energy ◽

High Activation ◽

X Ray ◽

High Activation Energy ◽

Highly Sensitive ◽

Here, we constructed Pb-free Cu-DABDT-MOFs-based (DABDT = 2,5-diamino-1,4-benzenedithiol dihydrochloride) X-ray detectors. Combined with the advantage of high activation energy, Cu-DABDT-MOFs-based detector can effectively generate and capture electron under X-ray exposure...