N‐Based Rare Earth Complexes

Zhang, Xiaomei; Jiang, Jianzhuang

doi:10.1002/9780470824870.ch4

Cited by 7 publications

(4 citation statements)

References 71 publications

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“…Complexes of metals with large coordination numbers do not need much energy to reorganize one polyhedron to another. Common organic molecules used to construct lanthanide complexes are polydentate ligands (i.e., carboxylates), pyridine ligands, porphyrins, silylamides, aliphatic amides, and Schiff base ligands . Complexation with Schiff base ligands has been extensively developed to synthesize macrocyclic complexes.…”

Section: Lanthanides In Chemistry: Synthesis Of Lanthanide Complexesmentioning

confidence: 99%

Lanthanide Chemistry: From Coordination in Chemical Complexes Shaping Our Technology to Coordination in Enzymes Shaping Bacterial Metabolism

2016

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Lanthanide chemistry has only been extensively studied for the last 2 decades, when it was recognized that these elements have unusual chemical characteristics including fluorescent and potent magnetic properties because of their unique 4f electrons.1,2 Chemists are rapidly and efficiently integrating lanthanides into numerous compounds and materials for sophisticated applications. In fact, lanthanides are often referred to as "the seeds of technology" because they are essential for many technological devices including smartphones, computers, solar cells, batteries, wind turbines, lasers, and optical glasses.3-6 However, the effect of lanthanides on biological systems has been understudied. Although displacement of Ca by lanthanides in tissues and enzymes has long been observed,7 only a few recent studies suggest a biological role for lanthanides based on their stimulatory properties toward some plants and bacteria.8,9 Also, it was not until 2011 that the first biochemical evidence for lanthanides as inherent metals in bacterial enzymes was published.10 This forum provides an overview of the classical and current aspects of lanthanide coordination chemistry employed in the development of technology along with the biological role of lanthanides in alcohol oxidation. The construction of lanthanide-organic frameworks will be described. Examples of how the luminescence field is rapidly evolving as more information about lanthanide-metal emissions is obtained will be highlighted, including biological imaging and telecommunications.11 Recent breakthroughs and observations from different exciting areas linked to the coordination chemistry of lanthanides that will be mentioned in this forum include the synthesis of (i) macrocyclic ligands, (ii) antenna molecules, (iii) coordination polymers, particularly nanoparticles, (iv) hybrid materials, and (v) lanthanide fuel cells. Further, the role of lanthanides in bacterial metabolism will be discussed, highlighting the discovery that lanthanides are cofactors in biology, particularly in the enzymatic oxidation of alcohols. Finally, new and developing chemical and biological lanthanide mining and recycling extraction processes will be introduced.

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Section: Lanthanides In Chemistry: Synthesis Of Lanthanide Complexesmentioning

confidence: 99%

Lanthanide Chemistry: From Coordination in Chemical Complexes Shaping Our Technology to Coordination in Enzymes Shaping Bacterial Metabolism

2016

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“…Rare-earth organic complexes have been emerging as competent catalysts for several important organic transformations, 7 including C–H functionalisation 8 and polymerisation reactions. 9 The development of this area, in particular C–H functionalisation, heavily relies on the use of cyclopentadienyl (Cp) and its analogues as ancillary ligands.…”

Section: Introductionmentioning

confidence: 99%

Regioselective C–H alkylation of anisoles with olefins by cationic imidazolin-2-iminato scandium(iii) alkyl complexes

et al. 2023

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“…Lanthanide(III) ions, being hard Lewis acids, prefer to bind hard bases possessing oxygen-donor groups [22,30]. The coordination number of lanthanides may be even 12, but 8 and 9 are most common, and they are advantageous for the formation of sandwich-type complexes with various macrocycles, producing cubic or square antiprism polyhedra [31,32]. In the absence of a hard basis, Ln 3+ ions can be coordinated to other types of ligands, such as N-donor porphyrins [33].…”

Section: Introductionmentioning

confidence: 99%

Formation, Photophysics, and Photochemistry of Anionic Lanthanide(III) Mono- and Bisporphyrins

et al. 2019

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Since water-soluble porphyrin complexes of lanthanides(III) have proved to be promising for medical applications (e.g., luminescence imaging, photodynamic therapy, and theranostics), the investigation of the formation, photophysical, and photochemical properties of such coordination compounds provides useful pieces of information for their potential usage. Steady-state and time-resolved fluorometry, UV–Vis absorption spectroscopy, and continuous-wave photolysis were utilized for this purpose. 5,10,15,20-Tetrakis(4-sulfonatophenyl)porphyrin formed mono- and bisporphyrin complexes with samarium(III), europium(III), and gadolinium(III) as representatives in the middle of the lanthanide series. The special photoinduced behavior of these compounds was mostly determined by the position of the metal center, which was located out of the ligand plane, thus distorting it. Besides, the photochemical and, especially, photophysical features of the corresponding mono- and bisporphyrin complexes were similar because, in the latter species, two monoporphyrins were connected by a weak metal bridge between the peripheral sulfonato substituents (tail-to-tail dimerization). The formation of these coordination compounds and the transformation reactions between the mono- and bisporphyrins were rather slow in the dark at room temperature. These processes were accelerated by visible irradiation. However, dissociation and, especially, redox degradation were the main photoreactions in these systems, although with low quantum yields. Additionally, depending on the excitation wavelength, new types of photoproducts were also detected.

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N‐Based Rare Earth Complexes

Cited by 7 publications

References 71 publications

Lanthanide Chemistry: From Coordination in Chemical Complexes Shaping Our Technology to Coordination in Enzymes Shaping Bacterial Metabolism

Lanthanide Chemistry: From Coordination in Chemical Complexes Shaping Our Technology to Coordination in Enzymes Shaping Bacterial Metabolism

Regioselective C–H alkylation of anisoles with olefins by cationic imidazolin-2-iminato scandium(iii) alkyl complexes

Formation, Photophysics, and Photochemistry of Anionic Lanthanide(III) Mono- and Bisporphyrins

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