Near-Infrared Emissive Lanthanide Metal–Organic Frameworks for Targeted Biological Imaging and pH-Controlled Chemotherapy

<div>Tetrathiafulvalene-Lanthanide (TTF-Ln) Metal-Organic Frameworks (MOFs) are an interesting class of multifunctional materials in which porosity can be combined with electronic properties such as electrical conductivity, redox activity, luminescence and magnetism. Herein we report a new family of isostructural TTF-Ln MOFs, denoted as <b>MUV-5(Ln)</b> (Ln = Gd, Tb, Dy, Ho, Er), exhibiting semiconducting properties as a consequence of the short intermolecular S···S contacts established along the chain direction between partially oxidised TTF moieties. In addition, this family shows photoluminescence properties and single-molecule magnetic behaviour, finding near-infrared (NIR) photoluminescence in the Yb/Er derivative and slow relaxation of the magnetisation in the Dy and Er derivatives. As such properties are dependent on the electronic structure of the lanthanide ion, we emphasise the immense structural, electronic and functional versatility of this class of materials.</div>

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Two Lanthanide Metal–Organic Frameworks Based on Semi-Rigid T-Shaped Tricarboxylate Ligand: Syntheses, Structures, and Properties

Polymers ◽

10.3390/polym11050868 ◽

2019 ◽

Vol 11 (5) ◽

pp. 868

Author(s):

Yun-Shan Xue ◽

Zhuo-Lin Chen ◽

Youzhen Dong ◽

Wei-Wei Cheng

Keyword(s):

Near Infrared ◽

Metal Organic Frameworks ◽

Infrared Emission ◽

Tripodal Ligand ◽

Structures And Properties ◽

3D Network ◽

Metal Organic ◽

Lanthanide Metal ◽

Near Infrared Emission ◽

Solvothermal Conditions

By using a semi-rigid tripodal ligand 5-(4-carboxybenzyloxy)isophthalic acid (H3L) and lanthanide metal ions (Nd3+, Tb3+), two novel lanthanide metal–organic frameworks, namely, {[Nd2L2(DMF)4] DMF}n (1), and {TbL(DMF)(H2O)}n (2), were synthesized under mild solvothermal conditions and structurally characterized by X-ray single crystal diffraction. Compounds 1 and 2 are isostructural, in which L3– ligands linked dinuclear lanthanide metal–carboxylate units to form non-interpenetrated 3D network with (3,6)-connected topology. Luminescent investigations reveal that compound 1 displays the near-infrared emission at room temperature, and compound 2 can be employed as selective probe for Cr2O72− anion in aqueous solution based on luminescence quenching. Moreover, compound 2 exhibits catalytic activity for cyclo-addition of CO2 and epoxides under relatively mild conditions.

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Electronic, Structural and Functional Versatility in Tetrathiafulvalene-Lanthanide Metal-Organic Frameworks

10.26434/chemrxiv.9037352 ◽

2019 ◽

Author(s):

Javier Castella-Gil ◽

Samuel Mañas-Valero ◽

Iñigo J. Vitórica-Yrezábal ◽

Duarte Ananias ◽

João Rocha ◽

...

Keyword(s):

Single Molecule ◽

Near Infrared ◽

Metal Organic Frameworks ◽

Magnetic Behaviour ◽

Redox Activity ◽

New Family ◽

Semiconducting Properties ◽

Metal Organic ◽

Lanthanide Metal ◽

Functional Versatility

<div>Tetrathiafulvalene-Lanthanide (TTF-Ln) Metal-Organic Frameworks (MOFs) are an interesting class of multifunctional materials in which porosity can be combined with electronic properties such as electrical conductivity, redox activity, luminescence and magnetism. Herein we report a new family of isostructural TTF-Ln MOFs, denoted as <b>MUV-5(Ln)</b> (Ln = Gd, Tb, Dy, Ho, Er), exhibiting semiconducting properties as a consequence of the short intermolecular S···S contacts established along the chain direction between partially oxidised TTF moieties. In addition, this family shows photoluminescence properties and single-molecule magnetic behaviour, finding near-infrared (NIR) photoluminescence in the Yb/Er derivative and slow relaxation of the magnetisation in the Dy and Er derivatives. As such properties are dependent on the electronic structure of the lanthanide ion, we emphasise the immense structural, electronic and functional versatility of this class of materials.</div>

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