[신간의 별자리x] 우리/미술, 그리고 ‘슬픔의 박물관’

The luminescence response application in chemical sensing by metal–organic frameworks (MOFs) and their hybrid materials has been reported extensively in recent years. However, the reviews on this topic are mainly focused on the sensing materials (MOFs and their functionalized hybrid materials) and analytes (all types of species). In this comprehensive review, the luminescence response mode and chemical sensing mechanism for lanthanide-functionalized MOF hybrids (abbreviated as LnFMOFH) are systematically summarized. Specifically, ten sections are subdivided, and importantly involve three main topics. Firstly, LnFMOFH and the luminescence responsive chemical sensing for these hybrids are introduced. Secondly, three single luminescence response modes, including “Turn-Off”, “Turn-On” “Turn–Off–On” and dual mode, as ratiometric luminescence (RL) for chemical sensing in LnFMOFH materials are summarized. Thirdly, some types of chemical sensing mechanisms observed in LnFMOFH materials are outlined, which involve the ligand–metal energy transfer (LMET) for the luminescence response in chemical sensing of enhanced or weakened analytes; the fluorescence (Forster) resonance energy transfer (FRET) and photo-induced electronic transfer (PET) mechanism depending on the energy match between the probe and analyte; and some special chemical interactions for their luminescence response upon chemical sensing, such as hydrogen bonding interaction, coordination interaction and other reactions. Finally, the conclusion and prospects are given for this topic. It needs to be noted that pure lanthanide MOFs (lanthanide ions as the framework metal, including mixed lanthanide MOFs) are not the topic of this review and are only mentioned for background knowledge. Herein, LnFMOFH materials in which the lanthanide ions behave only as photoactive species to functionalize MOF units via post-synthetic modification (PSM) by researchers are the emphasis of this review.

Luminescence response mode and chemical sensing mechanism for lanthanide-functionalized metal–organic framework hybrids

Advances in fluorescent and colorimetric sensors for anionic species

We present a comprehensive investigation of the magnetic and optical properties of an ytterbium complex, which combines two desirable and practical features into a single molecular system. Based upon YbIII ions that promote near-infrared optical activity and a chemical backbone that is ideal for an in-depth understanding of the magnetic behaviour, we have designed a multifunctional opto-magnetic species that operates as a luminescent thermometer and as a single-molecule magnet (SMM). Our magnetic investigations, in conjunction with ab initio calculations, reveal one of the highest energy barriers reported for an YbIII-based complex. Moreover, we correlate this anisotropic barrier with the emission spectrum of the compound, wherein we provide a complete assignment of the energetic profile of the complex. Such studies lay the foundation for the design of exciting multi-faceted materials that are able to retain information at the single-molecule level and possess built-in thermal self-monitoring capabilities.

/pdf/exploring-the-dual-functionality-of-an-ytterbium-complex-for-3kzxxv1u91.pdf

Exploring the dual functionality of an ytterbium complex for luminescence thermometry and slow magnetic relaxation

A reversible salamo-like probe (H2L) and its nickel(II) complex which could be fully characterized by various physicochemical and spectroscopic techniques. Furthermore, the solid-state crystal structure of the nickel(II) complex along with detailed structural analysis using single crystal X-ray crystallography. The developed probe could be used as an efficient fluorogenic probe to detect Ni2+ ion in aqueous medium. Subsequently, the in situ generated complex exhibited a high sensitivity and selectivity to HPO42− ion with detection limit of 3.42 × 10−8 M. The sensing mechanism of H2L towards Ni2+ ion and sequential detection towards HPO42− ion are well studied by UV–Vis and ESI mass methods. The practical applicability values of this probe have been examined by test paper and reversible cycle. 

A new reversible aldehyde-appended salamo-like fluorogenic probe for cascade sensing of Ni and HPO42- ions in aqueous medium

Mixed lanthanide coordination polymers for temperature sensing and enhanced NdIII NIR luminescence

A monocationic ZnII tetrahedral cluster, [Zn4L3(μ3-OH)]·NO3·125H2O (Zn4L3) based on a new salicylamide imine ligand H2L, H2L = 1-(2-hydroxy-3-methoxy-benzamido)-3-(2-hydroxy-3-methoxy-benzylideneamino)-propane, has been prepared Single crystal X-ray analysis reveals that three deprotonated ligands L2– chelate three Zn(II) centres with their salicylamide moiety in such a way that the three salicylimine groups attached to the other side of the three chelates are converged to bind another Zn(II) centre to provide a tetrahedral cluster with two phenyl groups of the same ligand L2– being close enough to present a strong intramolecular π⋯π stacking effect Fluorescence studies indicate that Zn4L3 is stable in water and exhibits highly sensitive and selective recognition of phosphates against other common anions including CO32–, HCO3–, NO3–, F−, Cl−, Br−, I−, HSO4–, SO42–, OAc−, BF4–, ClO4– and CF3SO3– in HEPES buffer solution (pH = 74) + DMSO (V : V = 1 : 9) The excellent sensing capability of Zn4L3 for phosphate against other common anions with a low detection limit of 015 μM renders it a candidate probe for phosphate detection Furthermore, the observed fluorescence quenching responses of Zn4L3 towards phosphates were highly reversible The possible sensing mechanisms for phosphate detection by Zn4L3 was investigated by means of 1H NMR, UV-Vis spectra and high-resolution ESI-MS spectra and the results indicate that phosphates could exclusively decompose Zn4L3 to release H2L in HEPES buffer solution (pH = 74) + DMSO (V : V = 1 : 9)

A cationic tetrahedral Zn(ii) cluster based on a new salicylamide imine multidentate ligand: synthesis, structure and fluorescence sensing study.

It is common knowledge that the spatial structure of substrates is the major influencing factor in DNA binding. To tune the binding affinity of DNA, a new 4-acylpyrazolone derivative ligand, (2-hydroxy-N′-((5-hydroxy-3-methyl-1-(4-nitrophenyl)-4,5-dihydro-1H-pyrazol-4-yl)(phenyl)methylene)benzohydrazide) (H2L) and its three complexes have been prepared and well characterized. Reaction of H2L with CuCl2 resulted in a mononuclear compound with tetra-coordinated quadrilateral plane, [Cu(HL)Cl] (1). When H2L was coordinated to Cu(OAc)2, a dinuclear Cu(II) compound with chemical formula of [Cu2L2(CH3OH)2]·CH3OH (2) was obtained, and the coordination geometry of Cu(II) is a square pyramid. Upon assembly of H2L with Mn(OAc)2, a quite different dinuclear compound with chemical composition of [Mn2L2(O CH3)2(H2O)2]·CH3OH (3) was afforded, where Mn(III) displayed distorted octahedral configurations. DNA binding studies were performed on H2L and its three complexes by means of electron absorption titration and EB–DNA competition experiments, and the results indicate they all bind DNA in an intercalation mode, and their binding affinity follows the order of 1 > 2 > 3 > H2L. In addition, time-dependent density functional theory (TD-DFT) calculations were performed for H2L and its three complexes to better clarify the electronic transitions in the UV-vis spectra.

Tuned structure and DNA binding properties of metal complexes based on a new 4-acylpyrazolone derivative

Two dinuclear lanthanide complexes based on a salicylamide imine multidentate ligand: Synthesis, structure and NIR emission properties

A Cu(II) complex based on a pyrazolone derivative, 2-hydroxy-N′-((1-(4-methoxyphenyl)-3methyl-5-oxo-4,5-dihydro-1H-pyrazol-4-yl)(phenyl)methylene)benzohydrazide (H2L), has been prepared. IR spectra...

Syntheses, structure, DNA-binding and DFT studies of a Cu(II) complex based on a pyrazolone derivative

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