Organosamarium Complex Research Articles

Synthesis, X-ray crystal structure and determination of non-covalent interactions through Hirshfeld surface analysis of a pure red emitting asymmetrical octacoordinated Sm(III) complex

A new organo-samarium complex [Sm(tfac)3(DPEPO)] (Sm1) has been synthesized by incorporating trifluoroacetylacetone (tfac) as the primary antenna ligand and bis(2-(diphenylphosphino)phenyl)ether oxide (DPEPO) as the ancillary ligand. The structure of the complex was established by single crystal X-ray diffraction (SC-XRD) analysis, which shows that the coordination sphere is composed of a EuO6O2 core (octacoordinated). Continuous shape measures (CShMs) further revealed that the geometry around Sm(III) is trigonal dodecahedral with approximate D2d-symmetry. Different non-covalent interactions (NCIs) and their % contribution to the supramolecular structure and their role in stabilizing the structure were determined by Hirshfeld surface analysis. Photophysical properties of the complex were determined in the solid-state and in DCM solution. The complex emits brilliant red emission in the solid-state and in DCM solution with excited state lifetime in microsecond regime and relative quantum yield of 2.5±10 % in solution.

Reactivity of (C5Me5)2Sm(THF)2 with Nitriles: C−C Bond Cleavage To Form Cyanide Complexes

The divalent organosamarium complex (C5Me5)2Sm(THF)2 (1) reacts in toluene with Me3CCN to form the insoluble trivalent cyanide complex [(C5Me5)2SmCN]n (2). The Me3CCN reaction was found to proceed ...

Observation of near infrared and enhanced visible emissions from electroluminescent devices with organo samarium(III) complex

Samarium (dibenzoylmethanato)3 bathophenanthroline (Sm(DBM)3 bath) was employed as an emitting and electron transport layer in organic light emitting diodes (OLEDs), and narrow electroluminescent (EL) emissions of a Sm3+ ion were observed in the visible and near infrared (NIR) region, differing from those of the same devices with Eu3+- or Tb3+-complex EL devices with the same structure. The EL emissions of the Sm3+-devices originate from transitions from 4G5/2 to the lower respective levels of Sm3+ ions. A maximum luminance of 490 cd m−2 at 15 V and an EL efficiency of 0.6% at 0.17 mA cm−2 were obtained in the visible region, and the improved efficiency should be attributed to introducing a transitional layer between the N,N′-diphenyl-N,N′-bis(3-methylphenyl)-1,1′-diphenyl-4,4′-diamine (TPD) film and the Sm(DBM)3 bath film and the avoidance of interfacial exciplex emission in devices. Sharp emissions of Sm3+ ions in the NIR region were also observed under a lower threshold value less than 4.5 V.

Efficient organic electroluminescent devices based on an organosamarium complex

Several organic electroluminescent devices with different device structures were fabricated based on an organosamarium complex Sm(HFNH) 3phen[HFNH=4, 4, 5, 5, 6, 6, 6-heptafluoro-1-(2-naphthyl)hexane-1, 3-dione; phen=1, 10-phenanthroline] as emitter. Their electroluminescent properties were investigated in detail. Although the devices with the optimal structure ITO/TPD (50 nm)/ Sm(HFNH) 3phen ( x wt%):CBP (50 nm)/BCP (20 nm)/AlQ (30 nm)/LiF (1 nm)/Al (200 nm) show high brightness (more than 400 cd/m 2) and high current efficiency (about 1 cd/A), there are emissions from CBP, BCP and even from AlQ existing in the electroluminescence (EL) spectra besides emission from Sm(HFNH) 3phen. The reason to this was discussed. The device with the structure ITO/TPD (50 nm)/Sm(HFNH) 3phen (50 nm)/AlQ (30 nm)/LiF (1 nm)/Al (200 nm) exhibits the maximum brightness of 118 cd/m 2 and current efficiency of 0.029 cd/A, and shows emissions from AlQ and Sm(HFNH) 3phen at high voltages. However, with the BCP hole-block layer added, the device [ITO/TPD (50 nm)/Sm(HFNH) 3phen (50 nm)/BCP (20 nm)/AlQ (30 nm)/LiF (1 nm)/Al (200 nm)] exhibits pure Sm 3+ emission in the EL spectra even at high voltages, with the maximum current efficiency of 0.29 cd/A and brightness of 82 cd/m 2.

Reductive disproportionation of carbon dioxide by a Sm(ii) complex: Unprecedented f-block element reactivity giving a carbonate complex

A macrocyclic organosamarium(II) complex has been shown to provide the first example of the reductive disproportionation of carbon dioxide, giving a bimetallic carbonate complex and carbon monoxide in a facile reaction under ambient conditions.

Synthesis, Structural Characterization, and Reactivity of Rare-Earth Complexes Derived from A New Phosphorus-Bridged Versatile Ligand, iPr2NP(C9H7)(C2B10H11)

New phosphorus-bridged ligands incorporating both indenyl and carboranyl moieties were prepared. Reaction of iPr2NP(C9H7)Cl (1) with 1 equiv of Li2C2B10H10 gave, after treatment with 1 equiv of n-BuLi, the dilithium salt [iPr2NP(C9H6)(C2B10H10)]Li2(OEt2)1.5 (2). 2 can be conveniently converted into its neutral counterpart iPr2NP(C9H7)(C2B10H11) (4) by treatment with excess dry Me3NHCl in CH2Cl2. Mixing 2 and 4 in a 1:1 molar ratio afforded quantitatively the monolithium salt [iPr2NP(C9H6)(C2B10H11)]Li(DME)3 (3). Reaction of YbI2 with 1 equiv of 2 gave the organoytterbium(II) complex [η5:σ-iPr2NP(C9H6)(C2B10H10)]Yb(DME)2 (5). 5 reacted further with 1 equiv of 3 to afford the organoytterbium(III) complex [{η5:σ-iPr2NP(C9H6)(C2B10H10)}2Yb][Li(THF)3(Et2O)] (6). In sharp contrast, treatment of SmI2 with 1 equiv of 2 generated the trivalent organosamarium complex [{η5:σ-iPr2NP(C9H6)(C2B10H10)}2Sm][Li(DME)3] (7). Reaction of LnCl3 with 2 equiv of 2 gave the ionic complexes [{η5:σ-iPr2NP(C9H6)(C2B10H10)}2Ln][Li(L...

Hydrolytic Reactivity of a Samarium(II) Organometallic Complex: Synthesis and Structure of a Hexametallic Organosamarium Oxide Hydroxide, [(C5Me5)Sm]6O9H6

Controlled hydrolysis of the divalent organosamarium complex (C5Me5)2Sm(THF)2 in THF forms [(C5Me5)Sm]6O9H6, 1, which has a solid-state structure consisting of a distorted octahedral array of six [(C5Me5)Sm]2+ units connected by eight triply bridging oxygens and a central oxygen.

Synthesis of monodisperse poly(butyl acrylate) initiated by SmMe(C5Me5)2(THF) and its adhesive properties after crosslinking by electron-beam irradiation

Polymerization reactions of butyl acrylate (BuA) were carried out using an organosamarium complex, SmMe(C5Me5)2(THF), as an initiator. Polymerization proceeds quantitatively to give high number-average molecular mass polymers (Mn > 200,000) and narrow molecular weight distributions (Mw/Mn < 1.07). Irradiation of the resulting poly(BuA) with an electron beam (EB) gave crosslinked poly(BuA). Improved viscoelastic and adhesive properties of these polymers were useful for high-temperature applications. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 432–437, 2001

Synthesis of end-functionalized low molecular weight poly(butyl acrylate) and its elongation using a diisocyanate

Bifunctionalized poly(butyl acrylate) and poly(methyl methacrylate) were synthesized by the polymerization of butyl acrylate or methyl methacrylate using an organosamarium complex, [SmMe(C 5Me 5) 2(CH 2–CH–CHCH 2)] 2, as an initiator followed by the insertion of aldehydes. The polymerization proceeds quantitatively to afford the hydroxy-end functionalized polymer ( M n>4120) with narrow molecular weight distributions ( M w/ M n<1.13). The attempted chain elongation of the resulting polymer with 4,4′-methylenebis(phenylisocyanate) has however failed, while the chain extension was realized by the reaction of poly(ϵ-caprolactone- co-butyl acrylate- co-ϵ-caprolactone) ( M n>15,200, M w/ M n<1.23) with a diisocyanate affording the desired high solid paint with M n of 87,600 using a limited amount of THF as a solvent.

Syntheses and adhesion properties of novel syndiotactic block copolymers of alkyl (meth)acrylate with methacrylic acid and its analogues

Block copolymerizations of (1) methyl methacrylate (MMA) with butyl acrylate (BuA), (2) trimethylsilyl methacrylate (TMSMA) with MMA, and (3) TMSMA with BuA were carried out using an organosamarium complex, SmMe(C 5Me 5) 2(THF), as an initiator. All copolymerizations proceeded quantitatively in a short period and the resulting polymers exhibit a high molecular weight ( M n>200 000) with narrow molecular weight distributions ( M w/ M n<1.5). The resulting poly(TMSMA) block in the copolymers was hydrolyzed with aq. HCl solution to afford the corresponding poly(methacrylic acid) block. The viscoelastic and adhesive properties of these block copolymers proved to be very useful, especially in the high temperature range, compared with those obtained using conventional radical initiators.

Synthesis and crystal structure of an organolanthanide fluoride, [{(Me3Si)2C5H3}2Sm(μ-F)

Treatment of [(Me 3 Si) 2 C 5 H 3 ] 2 SmI(THF) with stoichiometric amounts of AgSbF 6 in dry diethyl ether, or reaction of [(Me 3 Si) 2 C 5 H 3 ] 3 Sm with one equivalent of Me 3 NHF in dry 1,2-dimethoxyethane afforded the dimeric complex [{(Me 3 Si) 2 C 5 H 3 } 2 Sm( μ -F)] 2 in good yield, which represents the first structurally characterized example of a fluoride-bridged organosamarium complex. It crystallizes in space group P 2 1 / n with a = 12.215(1)Å, b = 16.028(1)Å, c = 15.677(1)Å, β = 99.78(1)°, V = 3025(2)Å 3 , and Z = 2 for D calcd = 1.292 g cm −3 . Least squares refinement of the structural model based on 5471 reflections (| F | > 6.0 σ | F |) converged to R F = 0.040. The average Sm(1)—F distance is 2.302(3)Å.

Ein alter Ligand in neuer Umgebung: Dreifach verbrückendes O,Ó- Dimethyldithiophosphat im Organosamarium-Komplex [(C 5Me 5)Sm{S 2P(OMe) 2} 2] 2

The reaction of (C 5Me 5) 2Sm(THF) 2 ( 1) with [(MeO) 2P(S)S] 2 results in elimination of a C 5Me 5 ligand and formation of the dinuclear organosamarium(III) complex [(C 5Me 5)Sm{S 2P(OMe) 2} 2] 2 ( 2). The molecular structure of 2 was determined by X-ray diffraction. The most notable structural feature is the presence of triply bridging O,Ó-dimethyldithiophosphate ligands in which one of the methoxy groups is involved in the coordination to samarium.

Synthesis of an organolanthanoid complex with a novel high-strain anionic cyclohexen-4-yne ligand and crystal structure of [(η5-Cp)2Sm(η5-C6H5)(thf)

An organosamarium complex, [(η5-Cp)2Sm(η5-C6H5)(thf)], with a novel high-strain anionic cyclohexen-4-yne ligand, a new benzene isomer, has been synthesised.

Synthesis and reactivity of the cationic organosamarium(III) complex [(C5Me5)2Sm(THF)2][BPh4], including the synthesis and structure of a metallocene with an alkoxy-tethered C5Me5 ring, (C5Me5)2Sm[O(CH2)4C5Me5](THF)

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and reactivity of the cationic organosamarium(III) complex [(C5Me5)2Sm(THF)2][BPh4], including the synthesis and structure of a metallocene with an alkoxy-tethered C5Me5 ring, (C5Me5)2Sm[O(CH2)4C5Me5](THF)William J. Evans, Tamara A. Ulibarri, L. R. Chamberlain, Joseph W. Ziller, and Daniel Alvarez Jr.Cite this: Organometallics 1990, 9, 7, 2124–2130Publication Date (Print):July 1, 1990Publication History Published online1 May 2002Published inissue 1 July 1990https://doi.org/10.1021/om00157a024RIGHTS & PERMISSIONSArticle Views504Altmetric-Citations143LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (945 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts

Samarium complex is uniquely reactive

Chemists at the University of California, Irvine, have discovered a way to insert two carbon monoxide molecules into a carbon-carbon double bond by the use of an organosamarium complex. The net reaction converts an alkene to a bis-enolate. William J. Evans, a chemistry professor at Irvine, and Donald K. Drummond, a graduate student, worked with the divalent organosamarium complex bis(pentamethylcyclopentadienyl) samarium(II) bis(tetrahydrofuranate) or [C 5 (CH 3 ) 5 ] 2 -Sm(THF) 2 [ J. Am. Chem. Soc. , 110 , 2772 (1988)]. The structure of this complex is somewhat analogous to that of ferrocene—in which two parallel cyclopentadienyl groups sandwich an iron cation—in that the aromatic pentamethylcyclopentadienyl groups sandwich the samarium cation. In the samarium complex, however, the pentamethylcyclopentadienyl groups are not parallel to each other. Rather, they are tilted, allowing the samarium to bind to the oxygen atoms on two tetrahydrofuran groups. Evans and coworkers have shown that this samarium co...

Reinvestigation of a transmetallation synthesis of bis(cyclopentadienyl)samarium(II) and formation of a new soluble cyclopentadienylsamarium(II) compound

The transmetallation reaction between (C 5H 5) 2Hg and activated samarium metal in tetrahydrofuran (thf)/ether did not give (C 5H 5) 2Sm(thf) 2 but (C 5H 5) 3Sm(thf), whilst reduction of the last compound with potassium in thf gave KSm(C 5H 5) 3, a soluble organosamarium(II) complex.

Synthesis and x-ray crystallographic characterization of an oxo-bridged bimetallic organosamarium complex, [(C5Me5)2Sm]2(.mu.-O)

Synthesis and x-ray crystallographic characterization of an oxo-bridged bimetallic organosamarium complex, [(C5Me5)2Sm]2(.mu.-O)

Synthesis and x-ray crystal structure of a soluble divalent organosamarium complex

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTSynthesis and x-ray crystal structure of a soluble divalent organosamarium complexWilliam J. Evans, Ira Bloom, William E. Hunter, and Jerry L. AtwoodCite this: J. Am. Chem. Soc. 1981, 103, 21, 6507–6508Publication Date (Print):October 1, 1981Publication History Published online1 May 2002Published inissue 1 October 1981https://doi.org/10.1021/ja00411a046RIGHTS & PERMISSIONSArticle Views883Altmetric-Citations144LEARN ABOUT THESE METRICSArticle Views are the COUNTER-compliant sum of full text article downloads since November 2008 (both PDF and HTML) across all institutions and individuals. These metrics are regularly updated to reflect usage leading up to the last few days.Citations are the number of other articles citing this article, calculated by Crossref and updated daily. Find more information about Crossref citation counts.The Altmetric Attention Score is a quantitative measure of the attention that a research article has received online. Clicking on the donut icon will load a page at altmetric.com with additional details about the score and the social media presence for the given article. Find more information on the Altmetric Attention Score and how the score is calculated. Share Add toView InAdd Full Text with ReferenceAdd Description ExportRISCitationCitation and abstractCitation and referencesMore Options Share onFacebookTwitterWechatLinked InReddit PDF (326 KB) Get e-AlertsSupporting Info (1)»Supporting Information Supporting Information Get e-Alerts