Synthesis, spectral characterization, crystal structures of lanthanide(III) pyrrolidine dithiocarbamate complexes and their catalytic activity

Pitchaimani, Ponnuchamy; Lo, Kong Mun; Elango, Kuppanagounder P.

doi:10.1080/00958972.2015.1037299

Cited by 15 publications

(11 citation statements)

References 31 publications

(46 reference statements)

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“…The synthesis of complexes 4 (cycLn 1 -phLn 2 ) was achieved by coordinating lanthanide chloride with one equivalent of complex 3 and three equivalents of ammonium pyrrolidine-1-carbodithioate at room temperature, followed by precipitation with diethyl ether from methanol. The proton nuclear magnetic resonance ( 1 H NMR) spectra of the La motif structure showed that three pyrrolidine dithiocarbamates were coordinated to the complex, which is consistent with a previous report 32 . This synthetic strategy provides a platform to obtain hetero-dinuclear complexes that consist of chemically similar lanthanide ions, one of which is not present in both ligand structures.…”

Section: Resultssupporting

confidence: 91%

A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties

et al. 2018

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The optical thermometer has shown great promise for use in the fields of aeronautical engineering, environmental monitoring and medical diagnosis. Self-referencing lanthanide thermo-probes distinguish themselves because of their accuracy, calibration, photostability, and temporal dimension of signal. However, the use of conventional lanthanide-doped materials is limited by their poor reproducibility, random distance between energy transfer pairs and interference by energy migration, thereby restricting their utility. Herein, a strategy for synthesizing hetero-dinuclear complexes that comprise chemically similar lanthanides is introduced in which a pair of thermosensitive dinuclear complexes, cycTb-phEu and cycEu-phTb, were synthesized. Their structures were geometrically optimized with an internuclear distance of approximately 10.6Å. The sensitive linear temperature-dependent luminescent intensity ratios of europium and terbium emission over a wide temperature range (50–298K and 10–200K, respectively) and their temporal dimension responses indicate that both dinuclear complexes can act as excellent self-referencing thermometers. The energy transfer from Tb3+ to Eu3+ is thermally activated, with the most important pathway involving the 7F1 Eu3+ J-multiplet at room temperature. The energy transfer from the antenna to Eu3+ was simulated, and it was found that the most important ligand contributions to the rate come from transfers to the Eu3+ upper states rather than direct ligand–metal transfer to 5D1 or 5D0. As the first molecular-based thermometer with clear validation of the metal ratio and a fixed distance between the metal pairs, these dinuclear complexes can be used as new materials for temperature sensing and can provide a new platform for understanding the energy transfer between lanthanide ions.

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Section: Resultssupporting

confidence: 91%

A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties

et al. 2018

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“…So, the geometry optimization of the Sm 3+ complex was performed with initial coordinates taken from the crystallographic data of Sm(pdtc) 3 (phen). 24 From the other side, the experimental structural data were used as a benchmark for estimation of the calculated parameters. The Eu(pdtc) 3 (phen) complex was modeled based on our X-ray diffraction data, which predicted isostructural Sm 3+ and Eu 3+ complexes.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The crystal structure of the Sm(pdtc) 3 (phen) complex was reported previously with single crystals obtained by storing the dissolved complex in chloroform in an airtight bottle with diethyl ether. 24 In our work, single crystals of Sm(pdtc) 3 (phen) were prepared by recrystallization of the complex in acetonitrile solution. About 10 mg of the complex was partially dissolved in acetonitrile, leaving a small amount undissolved at the bottom acting as seeds.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The obtained crystallographic data for 1 reproduce the reported ones. 24 Although the X-ray structure of 1 is known, there are very interesting results extracted from a crystallographic point of view, which are almost never discussed in the literature. The Sm 3+ complex is a mononuclear mixed ligand compound, which crystallizes in the triclinic crystal system in the P1̅ space group, cell parameters a = 9.991( 4 S1 in the Supporting Information.…”

Section: ■ Introductionmentioning

confidence: 99%

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Effect of Pyrrolidinedithiocarbamate Ligand on the Luminescence Properties of Heteroligand Samarium and Europium Complexes: Experimental and Theoretical Study

Borrisov,

Tsvetkov,

Zahariev

et al. 2024

Inorg. Chem.

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The photophysical properties of two isostructural heteroligand lanthanide complexes of general formula Ln(pdtc) 3 (phen) (pdtc = pyrrolidinedithiocarbamate anion, phen = 1,10-phenanthroline), Ln = Sm 3+ (1), Eu 3+ (2)) were studied in solid state and dichloromethane (DCM) solution. The two lanthanide complexes were investigated by experimental techniques for structural (single-crystal X-ray diffraction analysis of 1, powder XRD, TG-DTA) and spectroscopic [electron paramagnetic resonance (EPR), infrared (IR), ultraviolet−visible (UV−vis), photoluminescence (PL)] characterization. DFT/TDDFT/ωB97xD and multireference SA-CASSCF/NEVPT2 calculations with perturbative spin−orbit coupling corrections were applied to construct the Jablonski energy diagrams and to discuss the excited state energy transfer mechanism with competing excited state processes and possible sensitized mechanism of metal-centered emission. The first excited state (S 1 ) involved in the excited state energy transfer L(antenna)-to-Ln was predicted to have interligand (pdtc-to-phen) charge transfer character in contrast to the previously predicted ligand-to-metal charge transfer character. The theoretical consideration showed similar relaxation paths and luminescence quenching channels and appropriate Donor*(phen)-Acceptor*(Ln 3+ ) energy gap for 1 and 2. The experimental measurements in the solid state, however, showed efficient luminescence and good ability to convert UV to visible light only for the Sm(pdtc) 3 (phen) complex. The minor emission of 2 was explained by partial reduction of Eu 3+ , confirmed by EPR and calculated electron density distribution data.

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“…The methylene (CH2) protons of pyrdtcligands gave two pseudo triplets around  3.8 and 1.3. In addition, in the spectrum of 3b three sharp resonances due to free ethanol are observed[23]. These spectral features of 3b and 3b' suggest that the EtOH (or MeOH) molecule in the 9:9-coordinate complex dissociates in a chloroform solution to exist as an 8:8-coordinate dinuclear bphz-bridged complex.3.4.2 UV-visible absorption and MCD spectraUV-visible absorption and MCD spectra of the pyrdtccomplexes, 1b-5b, were measured in CH2Cl2 solutions.…”

mentioning

confidence: 97%

Dinuclear lanthanoid(III) dithiocarbamato complexes bridged by (E)-N-benzylidenepicolinohydrazonate: Syntheses, crystal structures and spectroscopic properties

Yakubu

Suzuki

Kita

2019

Inorganica Chimica Acta

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E)-N-Benzylidenepicolinohydrazide (Hbphz) was used to synthesize a series of hydrazonatobridged homodinuclear Ln III 2 dithiocarbamato (RR'dtc -) complexes of the form [{Ln(RR' dtc)2}2(µ-bphz)2] {Ln = La, Pr, Nd, Sm or Eu; RR' = dimethyl-(Me2) or pyrrolidine-(pyr)}.X-ray crystallographic studies revealed that these complexes possessed a common head-to-tail type dinuclear structural motif in which two hydrazonato ligands bridged two Ln III centers in the -1 2 N(py),O:2 2 O,N(imine) mode and two RR'dtc ligands coordinated to each Ln III center. Interestingly, while the Sm III and Eu III complexes crystallized as simple 8:8-coordinate dinuclear molecules, the lighter Ln III (i.e. La III , Pr III and Nd III ) complexes afforded in some cases 9:9-coordinate molecules, where the ninth coordination site was occupied by a solvent ethanol or methanol molecule. Even for the lighter Ln III complexes, the complexes were solved in dichloromethane or chloroform as the 8:8-coordinate dimer, as revealed by 1 H NMR spectroscopy. In the UV-visible absorption and magnetic circular dichroism (MCD) spectra of the complexes, similar spectral patterns for ligand-centered and Laporte forbidden f-f transitions were observed. The MCD spectral studies demonstrated the characteristic magnetooptical behavior of the complexes.

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Synthesis, spectral characterization, crystal structures of lanthanide(III) pyrrolidine dithiocarbamate complexes and their catalytic activity

Cited by 15 publications

References 31 publications

A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties

A stoichiometric terbium-europium dyad molecular thermometer: energy transfer properties

Effect of Pyrrolidinedithiocarbamate Ligand on the Luminescence Properties of Heteroligand Samarium and Europium Complexes: Experimental and Theoretical Study

Dinuclear lanthanoid(III) dithiocarbamato complexes bridged by (E)-N-benzylidenepicolinohydrazonate: Syntheses, crystal structures and spectroscopic properties

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