Syntheses, crystal structures and spectroscopic properties of two Cu2+-doped single crystals containing 3,14-diethyl-2,6,13,17-tetraazatricyclo[16.4.0.07,12]docosane

Jeon, Jonghyoun; Moncóľ, Ján; Mazúr, Milan; Valko, Marián; Ryoo, Keon Sang; Choi, Jong‐Ha

doi:10.1016/j.molstruc.2019.127224

Cited by 11 publications

(5 citation statements)

References 27 publications

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“…Due to the flexibility of the mononucleating AN and cyclam ligands, a variety of different conformations and rotamers with and without an additional solvent molecule (CH 3 CN) binding to the Fe III center were needed to be considered. These contain the cyclam ligand to Fe in either a folded ( cis -V) conformation with alternating directions of the amino hydrogens (above vs below the ring) or a planar ( trans -III) conformation with propylene-linked amino hydrogens pointing in the same and ethylene-linked ones in different directions . One of the axial binding sites to Fe in trans -cyclam is occupied by a coordinating solvent molecule CH 3 CN, while solvent coordination at the cis binding sites is sterically hindered by the bound [Cu(AN)(O 2 )] moiety.…”

Section: Resultsmentioning

confidence: 99%

“…These contain the cyclam ligand to Fe in either a folded (cis-V) conformation with alternating directions of the amino hydrogens (above vs below the ring) or a planar (trans-III) conformation with propylene-linked amino hydrogens pointing in the same and ethylene-linked ones in different directions. 37 The same approach has been pursued for complex 2 (vide infra), in which the amino hydrogen of the AN ligand is replaced with a methyl group (MeAN). For each conformational combination, the lowest-energy structure, along with their relative energies, geometric parameters, Raman data of 18 O-sensitive modes, and UV−vis absorption spectra are presented in Table S1.…”

Section: ■ Introductionmentioning

confidence: 99%

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A Bioinspired Nonheme Fe^III–(O₂^2–)–Cu^II Complex with an S_t = 1 Ground State

Kass,

Katz,

Özgen

et al. 2024

J. Am. Chem. Soc.

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Cytochrome c oxidase (CcO) is a heme copper oxidase (HCO) that catalyzes the natural reduction of oxygen to water. A profound understanding of some of the elementary steps leading to the intricate 4e − /4H + reduction of O 2 is presently lacking. A total spin S t = 1 Fe III −(O 2 2− )−Cu II (I P ) intermediate is proposed to reduce the overpotentials associated with the reductive O−O bond rupture by allowing electron transfer from a tyrosine moiety without the necessity of any spin-surface crossing. Direct evidence of the involvement of I P in the CcO catalytic cycle is, however, missing. A number of heme copper peroxido complexes have been prepared as synthetic models of I P , but all of them possess the catalytically nonrelevant S t = 0 ground state resulting from antiferromagnetic coupling between the S = 1/2 Fe III and Cu II centers. In a complete nonheme approach, we now report the spectroscopic characterization and reactivity of the Fe III −(O 2 2− )−Cu II intermediates 1 and 2, which differ only by a single −CH 3 versus −H substituent on the central amine of the tridentate ligands binding to copper. Complex 1 with an end-on peroxido core and ferromagnetically (S t = 1) coupled Fe III and Cu II centers performs H-bonding-mediated O−O bond cleavage in the presence of phenol to generate oxoiron(IV) and exchange-coupled copper(II) and PhO • moieties. In contrast, the μ-η 2 :η 1 peroxido complex 2, with a S t = 0 ground state, is unreactive toward phenol. Thus, the implications for spin topology contributions to O−O bond cleavage, as proposed for the heme Fe III −(O 2 2− )−Cu II intermediate in CcO, can be extended to nonheme chemistry.

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Section: Resultsmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

A Bioinspired Nonheme Fe^III–(O₂^2–)–Cu^II Complex with an S_t = 1 Ground State

Kass,

Katz,

Özgen

et al. 2024

J. Am. Chem. Soc.

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“…In addition, the wide absorption peaks at 650-800 nm are vest in the absorption of Cu 2+ ions, which may be from the Cu 2+ ions in a quantum dot solution that is not completely purified. [25] In order to further study its fluorescence properties, the Commission International de L'Eclairage (CIE) chromaticity coordinates for the emission of the MA(Pb,Cu)Br 3 perovskite quantum dots under 400 nm excitation are shown in Fig. 3(a).…”

Section: Resultsmentioning

confidence: 99%

Study on MA(Pb,Cu)Br3 Provskite Nanocrystal with Both Controlled Color Emission and Improved Stability

Liu¹,

Ji²,

Li³

et al. 2020

ES Mater.Manuf.

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Organic-inorganic hybrid perovskite quantum dots have always been the focus of research in recent years. However, the toxic Pb 2+ in MAPbBr 3 (MA = CH 3 NH 3 +) quantum dots and low stability restrict the application in the field of lighting display. In order to solve this problem, the MA(Pb,Cu)Br 3 perovskite quantum dots with Pb 2+ replaced by non-toxic Cu 2+ were synthesized via the auxiliary ligand precipitation. The phase evolution, controlled-color and fluorescent properties were systematically studied. The photoluminescence (PL) spectra monitored at the wavelength of 400 nm showed that the fluorescence emission intensity of quantum dots gradually decreased with the increase of the concentration of Cu 2+ , and the phenomenon of blue shift appeared. Moreover, the decay lifetime decreased when the dopant concentration of Cu 2+ gradually increased. The influence mechanism was discussed in details. In order to improve the stability, the MA(Pb, Cu)Br 3 @SiO 2 quantum dots were prepared by the hydrolysis of tetramethyl orthosilicate (TMOS). Meanwhile, the effect of temperature on the fluorescence properties of quantum dots was investigated in detail. The high stability and low toxicity of the MA(Pb, Cu)Br 3 @SiO 2 quantum dots are expected to be used in the fields of lighting display and solar cells.

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“…Cyclam has a moderately flexible structure, and can adopt both planar (trans) and folded (cis) conformations in [CrL 2 (cyclam)] n+ (L = monodentate or bidentate/2) complexes (Poon & Pun, 1980). There are five conformational trans isomers for the macrocycle, which differ in the chirality of the sec-NH groups (Choi, 2009;Jeon et al, 2020). The trans-I, trans-II and trans-V conformations also can fold to form cis-I, cis-II and cis-V conformers, respectively (Subhan et al, 2011;Jeon et al, 2020).…”

Section: Chemical Contextmentioning

confidence: 99%

“…There are five conformational trans isomers for the macrocycle, which differ in the chirality of the sec-NH groups (Choi, 2009;Jeon et al, 2020). The trans-I, trans-II and trans-V conformations also can fold to form cis-I, cis-II and cis-V conformers, respectively (Subhan et al, 2011;Jeon et al, 2020). Knowledge of the conformation for the macrocyclic ligand including various counter-anions are important factors in developing new highly effective anti-HIV drugs (Ronconi & Sadler, 2007;De Clercq, 2010;Ross et al, 2012).…”

Section: Chemical Contextmentioning

confidence: 99%

Crystal structure of cis-(1,4,8,11-tetraazacyclotetradecane-κ⁴ N)bis(thiocyanato-κN)chromium(III) bromide from synchrotron X-ray diffraction data

Moon¹,

Choi²

2021

Acta Cryst E

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The crystal structure of the title complex, cis-[Cr(NCS)2(cyclam)]Br (cyclam = 1,4,8,11-tetraazacyclotetradecane, C10H24N4), has been determined from synchrotron X-ray data. The asymmetric unit contains one [Cr(NCS)2(cyclam)]+ cation and one bromide anion. The CrIII ion of the complex cation is coordinated by the four N atoms of the cyclam ligand and by two N-coordinating NCS groups in a cis arrangement, displaying a distorted octahedral coordination sphere. The Cr—N(cyclam) bond lengths are in the range 2.075 (3) to 2.081 (3) Å while the average Cr—N(NCS) bond length is 1.996 (16) Å. The macrocyclic cyclam moiety adopts the most stable cis-V conformation. The crystal structure is stabilized by intermolecular hydrogen bonds involving the cyclam N—H groups as donor groups, and the bromide anion and the S atom of one of the NCS ligands as acceptor groups.

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Syntheses, crystal structures and spectroscopic properties of two Cu2+-doped single crystals containing 3,14-diethyl-2,6,13,17-tetraazatricyclo[16.4.0.07,12]docosane

Cited by 11 publications

References 27 publications

A Bioinspired Nonheme Fe^III–(O₂^2–)–Cu^II Complex with an S_t = 1 Ground State

A Bioinspired Nonheme Fe^III–(O₂^2–)–Cu^II Complex with an S_t = 1 Ground State

Study on MA(Pb,Cu)Br3 Provskite Nanocrystal with Both Controlled Color Emission and Improved Stability

Crystal structure of cis-(1,4,8,11-tetraazacyclotetradecane-κ⁴ N)bis(thiocyanato-κN)chromium(III) bromide from synchrotron X-ray diffraction data

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Syntheses, crystal structures and spectroscopic properties of two Cu2+-doped single crystals containing 3,14-diethyl-2,6,13,17-tetraazatricyclo[16.4.0.07,12]docosane

Cited by 11 publications

References 27 publications

A Bioinspired Nonheme FeIII–(O22–)–CuII Complex with an St = 1 Ground State

A Bioinspired Nonheme FeIII–(O22–)–CuII Complex with an St = 1 Ground State

Study on MA(Pb,Cu)Br3 Provskite Nanocrystal with Both Controlled Color Emission and Improved Stability

Crystal structure of cis-(1,4,8,11-tetraazacyclotetradecane-κ4 N)bis(thiocyanato-κN)chromium(III) bromide from synchrotron X-ray diffraction data

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A Bioinspired Nonheme Fe^III–(O₂^2–)–Cu^II Complex with an S_t = 1 Ground State

A Bioinspired Nonheme Fe^III–(O₂^2–)–Cu^II Complex with an S_t = 1 Ground State

Crystal structure of cis-(1,4,8,11-tetraazacyclotetradecane-κ⁴ N)bis(thiocyanato-κN)chromium(III) bromide from synchrotron X-ray diffraction data