Luminescent Functional Metal–Organic Frameworks

Among the recent developments in metal-organic frameworks (MOFs), porous layered coordination polymers (CPs) have garnered attention due to their modular nature and tunable structures. These factors enable a number of properties and applications, including gas and guest sorption, storage and separation of gases and small molecules, catalysis, luminescence, sensing, magnetism, and energy storage and conversion. Among MOFs, two-dimensional (2D) compounds are also known as 2D CPs or 2D MOFs. Since the discovery of graphene in 2004, 2D materials have also been widely studied. Several 2D MOFs are suitable for exfoliation as ultrathin nanosheets similar to graphene and other 2D materials, making these layered structures useful and unique for various technological applications. Furthermore, these layered structures have fascinating topological networks and entanglements. This review provides an overview of different aspects of 2D MOF layered architectures such as topology, interpenetration, structural transformations, properties, and applications.

Two-Dimensional Metal-Organic Framework Materials: Synthesis, Structures, Properties and Applications.

Hexamethylenetetramine: An old new building block for design of coordination polymers

Development of materials for fluorescence imaging with a wide optical range is important for clinical applications. In this work, a solution synthesis method was used for making Ag–Ho, Ag–Sm, Ag–Zn, Ag–Cu Ag–Cs, Ag–Zr, Ag–Er, Ag–Y and Ag–Co metal organic compound nanoparticles. XRD, XPS and TEM were carried out for sample characterization. They showed broad fluorescence from the UV to NIR region. In particular, they presented near-infrared (NIR) fluorescence (800–1100 nm) when excitation light of 785 nm was used. Furthermore, a white-to-green or blue-to-white transition was observed when excitation light varied from 290 nm to 370 nm. Proof-of-concept experiments were performed via UV light (359–371 nm), blue light (450–490 nm), green light (540–552 nm) and NIR light (center wavelength = 785 nm) excitation with pig-kidney tissue samples. They showed potential for biomedical fluorescence imaging in the UV-Vis-NIR range.

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Synthesis of Ag-Ho, Ag-Sm, Ag-Zn, Ag-Cu, Ag-Cs, Ag-Zr, Ag-Er, Ag-Y and Ag-Co metal organic nanoparticles for UV-Vis-NIR wide-range bio-tissue imaging.

Three polyoxometalate-based inorganic–organic hybrid compounds constructed from silver(I)-L (L = N,N′-bis-pyridin-2-ylmethylene-hydrazine) species and saturated Keggin type polyoxoanions, {[Ag3L3](PW12O40)(CH3CN)(DMF)2.5}n (1), [Ag4L3(CH3CN)4][Ag2L(CH3CN)3](PMo12O40)2·CH3CN (2) and [(SiMo12O40){Ag2L(CH3CN)3}2]·(CH3CN)2 (3), have been synthesized and structurally characterized by IR spectroscopy, UV spectroscopy, thermogravimetric (TG) analyses and complete single crystal structure analyses. The structure of 1 containing [PW12O40]3− anions as templates exhibits a one-dimensional chain structure constructed by the coordination of a silver center and bis-bidentate bridging ligands with the pyridyl rings adopting a transoid configuration. Compound 2 displays an AB-type arrangement supramolecular structure, in which A is a two-dimensional sheet formed by linking the adjacent [Ag4L3(CH3CN)4]4+ units through the cooperativity of intermolecular π–π interactions and C–H⋯π interactions, while B is composed of [PMo12O40]3− anions and binuclear [Ag2L(CH3CN)4]2+ cations. Compound 3 exhibits a new bisupporting Keggin-polyoxometalate structure in which the [SiMo12O40]4− core supports two [Ag2L(CH3CN)3]2+ fragments in two opposite positions. The luminescent properties of L and 1–3 in the solid state were investigated.

Assembly of polyoxometalate-based inorganic–organic compounds from silver–Schiff base building blocks: synthesis, crystal structures and luminescent properties

Synthesis, crystal structure and luminescent properties of one coordination polymer of cadmium(II) with mixed thiocyanate and hexamethylenetetramine ligands

Synthesis, crystal structure and luminescent properties of a thiocyanato bridged two-dimensional heteronuclear polymeric complex of cadmium(II) and copper(II)

Synthesis, crystal structure and luminescent properties of two cadmium thiocyanate coordination polymers with benzylpyridyl cations

A series of metal–organic frameworks {[AgL1]ClO4}n (1), {[AgL12]BF4}n (2), {[AgL1(NO3)](CH3CH2OH)}n (3), {[ZnL12(NCS)2]CH3CN}n (4), [AgL2(NO3)]n (5), {[FeL22Cl2]·CH3CN}n (6), {[MnL22(NCS)2]·(CH3CH2OH)}n (7) and [ZnL22(NCS)2]n (8) have been synthesized and structurally characterized by IR spectroscopy, UV spectroscopy, thermogravimetric (TG) analyses, luminescent spectroscopy and complete single-crystal structure analyses, where L1 is (N′,N′-bis[1-(pyridin-4-yl)methylidene]benzil dihydrazone) and L2 is (N′,N′-bis[1-(pyridin-3-yl)methylidene]benzil dihydrazone), respectively. The structure of 1 exhibits a two-dimensional layer network featuring trimetal 36-membered non-planar macrocycles. Polymer 2 is a one-dimensional chain structure with tetranuclear metallacyclic rings. For polymer 3, each ligand acts as a bidentate ligand to bind two Ag(I) centers and each silver center is coordinated to two N-donors from two ligands forming a one-dimensional chain. Polymer 4 displays a two-dimensional layer network containing tetranuclear 68-membered metallocyclic rings. Polymers [AgL2(NO3)]n (5), {[FeL22Cl2]·CH3CN}n (6), {[MnL22(NCS)2]·(CH3CH2OH)}n (7) and [ZnL22(NCS)2]n (8) show all one-dimensional chain structures containing bimetallic 8-membered rings and tetrametallic 42-membered rings for 5, bimetallic 34-membered quadrangular rings for 6 and 7, and bimetallic 30-membered quadrangular rings for 8, respectively. The luminescent properties of L1, L2 and 1–8 in the solid state were investigated.

A series of metal–organic frameworks based on polydentate Schiff-base ligands derived from benzil dihydrazone: synthesis, crystal structures and luminescent properties

Synthesis, crystal structure and luminescent properties of a thiocyanato-bridged two-dimensional heteronuclear polymeric complex of cadmium(II) and nickel(II)

Wei-Li Shang

Papers

Synthesis, crystal structure and luminescent properties of one coordination polymer of cadmium(II) with mixed thiocyanate and hexamethylenetetramine ligands

Synthesis, crystal structure and luminescent properties of a thiocyanato bridged two-dimensional heteronuclear polymeric complex of cadmium(II) and copper(II)

Synthesis, crystal structure and luminescent properties of two cadmium thiocyanate coordination polymers with benzylpyridyl cations

A series of metal–organic frameworks based on polydentate Schiff-base ligands derived from benzil dihydrazone: synthesis, crystal structures and luminescent properties

Synthesis, crystal structure and luminescent properties of a thiocyanato-bridged two-dimensional heteronuclear polymeric complex of cadmium(II) and nickel(II)