Abstract
Lanthanide complexes with sulfonylamidophosphate‐type ligands: dibenzyl(phenylsulfonyl)amidophosphate (H
SB
) and di(4‐methylphenyl)‐phenylsulfonyl‐amidophosphate (H
SK
) have been ...synthesized and show promise as new sensitizers of visible and near‐infrared luminescence. They constitute a new part of coordination chemistry for this type of ligand, creating simultaneously a new class of lanthanide complexes with
π
‐conjugated ligands possessing the structural fragment SO
2
NHP(O). Two series of stable lanthanide complexes NaLn(
SB
)
4
(
1Ln
) and NaLn(
SK
)
4
(
2Ln
), where Ln=Nd
III
, Eu
III
, Gd
III
, Tb
III
, Er
III
, Yb
III
, were characterized by X‐ray structure analysis. The IR, absorption, emission, and excitation spectra at 293, 77, and 4 K, as well as luminescence decay times and emission quantum yields were used to characterize the complexes in the solid state. The relation between the crystal structure and its spectroscopic properties is also discussed. The influence of the π–π stacking interactions and a ligand‐to‐metal charge transfer state on ligand‐to‐metal energy transfer efficiency was demonstrated and discussed. Crystal‐field lines determined from absorption and fluorescence spectra of
2Nd
were used in computational analysis employing free‐ion operators, one‐electron crystal‐field operators, and two‐particle correlation crystal‐field operators. The performed analysis enabled the determination of the Hamiltonian parameters and an unambiguous assignment of 85 crystal‐field levels of Nd
III
ion with a mean error of 12.0 cm
−1
.
The crystal structure of the title compound, NaNd(C8H11NO5PS)4n, is composed of two types of crystallographically independent polymeric chains, A and B, respectively, which are formed by alternating ...anions and sodium cations. In both polymeric chains, NdIII ions are eight‐coordinated by O atoms belonging to the sulfonyl and phosphoryl groups of four bidentate chelate ligands. In chain A, the coordination polyhedron of the NdIII ion has a conformation intermediate between bicapped trigonal‐prismatic and square‐antiprismatic, and the NaI ion is coordinated by two N and four O atoms in a distorted octahedral geometry. In chain B, the coordination polyhedron of Nd is a slightly distorted square antiprism, and Na is coordinated by four O atoms in a distorted tetrahedral geometry.
In the title compound, Ho(C(6)H(12)Cl(3)N(3)O(2)P)(3)(C(18)H(15)OP), the Ho(III) ion is surrounded by six O atoms from the three bidentate N-bis-(dimethyl-amino)phosphino-yl-2,2,2-trichloro-acetamido ...ligands (L(-)) and by one O atom from the triphenyl-phosphine oxide ligand, with the formation of a distorted monocapped octa-hedron. In one ligand L(-), the trichloro-methyl group is rotationally disordered between two orientations in a 1:1 ratio, while two dimethyl-amino groups in another ligand L(-) are disordered between two conformations, each with the same 1:1 ratio.
N -[Bis(dimethylamino)phosphinoyl]-2,2,2-trichloroacetamide Amirkhanov, Oleksiy V.; Moroz, Olesia V.; Znovjyak, Kateryna O. ...
Acta crystallographica. Section E, Structure reports online,
05/2010, Letnik:
66, Številka:
5
Journal Article
Odprti dostop
In the title compound, C6H13Cl3N3O2P or CCl3C(O)NHP(O)(N(CH3)2), the phosphinoyl group is synclinal to the carbonyl group and acts as an acceptor for an intermolecular N—H...O hydrogen bond ...from the amide group as the donor.
The crystal structure of the title compound, U(NO(3))(2)O(2)(C(10)H(17)Cl(3)N(3)O(2)P)(2), is composed of centrosymmetric UO(2)(L)(2)(NO(3))(2) mol-ecules {L is ...N-bis-(pyrrolidin-1-yl)phosphor-yl-2,2,2-trichloro-acetamide, C(10)H(17)Cl(3)N(3)O(2)P}. The U(VI) ion, located on an inversion center, is eight-coordinated with axial oxido ligands and six equatorial oxygen atoms of the phosphoryl and nitrate groups in a slightly distorted hexa-gonal-bipyramidal geometry. One of the pyrrolidine fragments in the ligand is disordered over two conformation (occupancy ratio 0.58:0.42). Intra-molecular N-H⋯O hydrogen bonds between the amine and nitrate groups are found.
Lanthanide complexes with sulfonylamidophosphate-type li- gands: dibenzyl(phenylsulfonyl)amidophosphate (hsb) and di(4-methylphenyl)-phenylsulfonyl-amidophosphate (hsk) have been synthesized and show ...promise as new sensitizers of visi- ble and near-infrared luminescence. They constitute a new part of coordination chemistry for this type of ligand, creating simultaneously a new class of lanthanide complexes with ?- conjugated ligands possessing the structural fragment S02NHP(0). Two series of stable lanthanide complexes NaLn(sb)4 (ILn) and NaLn(sk)4 (2Ln), where Ln = Nd'", Eu1", Gd1", Tb1", Er1", Yb1", were characterized by X-ray structure analy- sis. The IR, absorption, emission, and excitation spectra at 293, 77, and 4 K, as well as luminescence decay times and emission quantum yields were used to characterize the complexes in the solid state. The relation between the crystal structure and its spectroscopic properties is also discussed. The influence of the jt-jt stacking interactions and a ligand-to-metal charge transfer state on ligand-to-metal energy transfer efficiency was demonstrated and discussed. Crystal-field lines determined from absorption and fluorescence spectra of 2Nd were used in computational analysis employing free-ion operators, one-elec- tron crystal-field operators, and two-particle correlation crystal- field operators. The performed analysis enabled the determina- tion of the Hamiltonian parameters and an unambiguous as- signment of 85 crystal-field levels of Nd1" ion with a mean error of 12.0 cm-1. PUBLICATION ABSTRACT
In the title compound, C(6)H(13)Cl(3)N(3)O(2)P or CCl(3)C(O)NHP(O)(N(CH(3))(2)), the phosphinoyl group is synclinal to the carbonyl group and acts as an acceptor for an inter-molecular N-H⋯O hydrogen ...bond from the amide group as the donor.
TRPV1 has been originally cloned as the heat and capsaicin receptor implicated in acute pain signalling, while further research has shifted the focus to its importance in chronic pain caused by ...inflammation and associated with this TRPV1 sensitization. However, accumulating evidence suggests that, apart from pain signalling, TRPV1 subserves many other unrelated to nociception functions in the nervous system. In the brain, TRPV1 can modulate synaptic transmission via both pre- and postsynaptic mechanisms and there is a functional crosstalk between GABA receptors and TRPV1. Other fundamental processes include TRPV1 role in plasticity, microglia-to-neuron communication, and brain development. Moreover, TRPV1 is widely expressed in the peripheral tissues, including the vasculature, gastrointestinal tract, urinary bladder, epithelial cells, and the cells of the immune system. TRPV1 can be activated by a large array of physical (heat, mechanical stimuli) and chemical factors (e.g., protons, capsaicin, resiniferatoxin, and endogenous ligands, such as endovanilloids). This causes two general cell effects, membrane depolarization and calcium influx, thus triggering depending on the cell-type diverse functional responses ranging from neuronal excitation to secretion and smooth muscle contraction. Here, we review recent research on the diverse TRPV1 functions with focus on the brain, vasculature, and some visceral systems as the basis of our better understanding of TRPV1 role in different human disorders.
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