Structural features and near infra-red (NIR) luminescence of isomeric Yb(<scp>iii</scp>) bipyridyl-N,N′-dioxide coordination polymers

Sequeira, Gail M.; Tan, Wayne Y.; Moore, Evan G.

doi:10.1039/c5dt01875g

Cited by 9 publications

(12 citation statements)

References 28 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Strikingly, well‐split peaks instead of single sharp transition are observed, with another weak band appears at 980 nm. A similar splitting has been reported previously, attributed to the crystal field or stark splitting . The characteristic NIR emissions in CP 12 demonstrate that the ligand transfers the absorbed energy effectively to the emitting level of Yb(III) centers.…”

Section: Resultssupporting

confidence: 86%

See 1 more Smart Citation

Syntheses, Crystal structures, Magnetisms and Luminescences of two Series of Lanthanide Coordination Polymers Based on Tricarboxylic Ligand

et al. 2017

View full text Add to dashboard Cite

Two series of twelve polycarboxylate lanthanide coordination polymers (CPs), namely, [Ln(cpida)(H2O)]n{Ln=La (1), Ce (2), Pr (3) and Nd (4)} and {[Ln(cpida)(H2O)]⋅2H2O}n {Ln=Sm (5), Eu (6), Gd (7), Tb (8), Dy (9), Ho (10), Er (11) and Yb (12)} {H3cpida=N‐(4‐carboxyphenyl) iminodiacetic acid}, have been synthesized by self‐assembly and characterized by IR, TGA, X‐ray crystallography, powder XRD and elemental analysis. CPs 1–4 and 5–12 are isomorphic respectively, featuring 2D double layer structures. In CPs 1‐4, each metal atom connects five [cpida]3− anions and each ligand is bound to five metal cations. However, in 5‐12 each [cpida]3− anion only connects four metal cations due to the lanthanide contraction. Further, PL spectra of CPs 6, 8 and 12 show the strong characteristic luminescence of Eu(III), Tb(III) and Yb(III) ions, respectively, suggesting that [cpida]3‐ is able to sensitize the luminescence of lanthanide ions efficiently. The magnetic properties of Gd (7) and Dy (9) complexes have also been investigated.

show abstract

Section: Resultssupporting

confidence: 86%

“…A similar splitting has been reported previously, attributed to the crystal field or stark splitting. [42][43][44][45] The characteristic NIR emissions in CP 12 demonstrate that the ligand transfers the absorbed energy effectively to the emitting level of Yb(III) centers.…”

Section: Photoluminescent Propertiesmentioning

confidence: 99%

Syntheses, Crystal structures, Magnetisms and Luminescences of two Series of Lanthanide Coordination Polymers Based on Tricarboxylic Ligand

et al. 2017

View full text Add to dashboard Cite

show abstract

“…Europium(III) nitrate pentahydrate [Eu(NO 3 ) 3 ·5H 2 O; CAS 63026-01-7], gadolinium(III) nitrate hexahydrate [Gd(NO 3 ) 3 ·6H 2 O; CAS 19598-90-4], potassium tetracyanoplatinate(II) hydrate {K 2 [Pt(CN) 4 ]· x H 2 O; CAS 38245-27-1}, potassium tetracyanopalladate(II) hydrate {K 2 [Pd(CN) 4 ]· x H 2 O; CAS 14516-46-2}, potassium dicyanoaurate(I) {K[Au(CN) 2 ]; CAS 13967-50-5}, and potassium dicyanoargentate {K[Ag(CN) 2 ]; CAS 506-61-6} were purchased from Sigma-Aldrich. The 4,4′-bipyridine N , N ′-dioxide (4,4′-bpdo) ligand was prepared according to the published procedure using 4,4′-bipyridine (98%, Alfa Aesar, CAS 553-26-4) as a starting material.…”

Section: Methodsmentioning

confidence: 99%

Europium(III) Photoluminescence Governed by d⁸–d¹⁰ Heterometallophilic Interactions in Trimetallic Cyanido-Bridged Coordination Frameworks

2020

View full text Add to dashboard Cite

We report an efficient pathway toward sensitization of red room temperature EuIII emission by the charge-transfer (CT) states related to d8–d10 heterometallophilic interactions achieved by the simultaneous application of tetracyanidometallates of PtII/PdII and dicyanidometallates of AuI/AgI in the construction of a trimetallic d–d–f assembly. The combination of Eu3+, [MII(CN)4]2– (M = Pt, Pd), and [MI(CN)2]− (M = Au, Ag) ions along with 4,4′-bipyridine N,N′-dioxide (4,4′-bpdo) results in four novel isostructural 2D {[EuIII(4,4′-bpdo)(H2O)2][MII(CN)4]}·[MI(CN)2]·H2O (MII/MI = Pt/Au, 1; Pt/Ag, 2; Pd/Au, 3; Pd/Ag, 4) coordination networks. They are built of hybrid coordination layers, based on cyanido-bridged {EuIII[MII(CN)4]} n square grids coexisting with metal–organic {EuIII(4,4′-bpdo)} n chains, with the further attachment of [MI(CN)2]− ions through metallophilic {MII–MI} interactions. This results in dinuclear {MIIMI} units generating an orange emissive metal-to-metal-to-ligand charge-transfer (MMLCT) state, whose energy is tuned by the applied d8–d10 metal centers. Thanks to these CT states, 1–4 exhibit room temperature red EuIII photoluminescence enhanced by energy transfer from {MIIMI} units, with the additional role of 4,4′-bpdo also transferring the energy to lanthanides. These donor CT states lying in the visible range successfully broaden the available efficient excitation range up to 500 nm. The overall emission quantum yield ranges from 8(1)% for 4 to 15(2)% for 1, with the intermediate values for 2 and 3 relatively high among the reported EuIII-based compounds with tetracyanido- and dicyanidometallates. We found that the sensitization efficiency is equally high for all compounds because of the similar energies of the CT states, while the main differences are related to the observed emission lifetimes ranging from ca. 80 μs for 4 to 120–130 μs for 2 and 3 to ca. 180 μs for 1. This phenomenon was correlated with the energies of the vibrational states, e.g., cyanide stretching vibrations, responsible for nonradiative deactivation of EuIII excited states, which are the highest for the Pd/Ag pair of 4 and the lowest for the Pt/Au pair in 1. Thus, the heaviest pair of PtII/AuI cyanide metal complexes is proven to be the best candidate for the sensitization of room temperature EuIII luminescence.

show abstract

“…We have previously reported [31] the structure and luminescence properties of a high connectivity (3 5 .4 14 .5 9 )(3 5 .4 13 .5 10 ) 2 coordination polymer network, [Yb(4,4'-bpdo) 4 ](CF 3 SO 3 ) 3 ] ∞ , which form upon reaction of Yb(CF 3 SO 3 ) 3 ·xH 2 O with 4,4'-bpdo over a period of ca. 2-3 weeks using CHCl 3 as a chlorinated anti-solvent.…”

Section: Syntheses and Structural Studiesmentioning

confidence: 98%

“…We have previously shown [31] that 4,4'-bpdo acts as a light harvesting antennae for sensitised Ln(III) emission, and solid state Near Infra-Red (NIR) emission spectra of 1-5 have been measured upon 360 nm excitation in the solid state at room temperature (see Fig. S1, Supp.…”

Section: Photoluminescencementioning

confidence: 99%

Structure and efficient luminescence upconversion of Ln(iii) aromatic N-oxide coordination polymers

Chong

Moore

2016

Dalton Trans.

Self Cite

View full text Add to dashboard Cite

A series of lanthanide-based coordination polymers {[Yb1-xErx(4,4'-bpdo)3(H2O)2](CF3SO3)3}∞ were synthesised by solvent diffusion techniques, where 4,4'-bpdo = 4,4'-bipyridine-N,N'-dioxide, and using differing mole fractions of Yb(iii) and Er(iii) which were systematically varied (x = 0, 0.05, 0.20, 0.50 and 1). All of the materials obtained were characterised using elemental analyses, single-crystal X-ray diffraction (SXRD) and solid-state photoluminescence studies. Structurally, the coordination polymers crystallise as an isomorphous series of infinite 2D sheets, which contain two inner sphere water molecules, and are isostructural with a previously characterised homometallic Yb(iii) compound. In addition to the normal Near Infra-Red (NIR) luminescence, these compounds also demonstrate upconversion emission upon 980 nm excitation. Upconversion luminescence measurements reveal visible emission in the red, green, and blue regions corresponding to the (2)H11/2→(4)I15/2, (4)F9/2→(4)I15/2 and (2)H9/2→(4)I15/2 transitions of the Er(iii) cation upon two and three-photon excitation. We also observed weak emission from the Er(iii) cation in the UV region for the first time in a Ln-MOF based material.

show abstract

Structural features and near infra-red (NIR) luminescence of isomeric Yb(iii) bipyridyl-N,N′-dioxide coordination polymers

Cited by 9 publications

References 28 publications

Syntheses, Crystal structures, Magnetisms and Luminescences of two Series of Lanthanide Coordination Polymers Based on Tricarboxylic Ligand

Syntheses, Crystal structures, Magnetisms and Luminescences of two Series of Lanthanide Coordination Polymers Based on Tricarboxylic Ligand

Europium(III) Photoluminescence Governed by d⁸–d¹⁰ Heterometallophilic Interactions in Trimetallic Cyanido-Bridged Coordination Frameworks

Structure and efficient luminescence upconversion of Ln(iii) aromatic N-oxide coordination polymers

Contact Info

Product

Resources

About

Structural features and near infra-red (NIR) luminescence of isomeric Yb(iii) bipyridyl-N,N′-dioxide coordination polymers

Cited by 9 publications

References 28 publications

Syntheses, Crystal structures, Magnetisms and Luminescences of two Series of Lanthanide Coordination Polymers Based on Tricarboxylic Ligand

Syntheses, Crystal structures, Magnetisms and Luminescences of two Series of Lanthanide Coordination Polymers Based on Tricarboxylic Ligand

Europium(III) Photoluminescence Governed by d8–d10 Heterometallophilic Interactions in Trimetallic Cyanido-Bridged Coordination Frameworks

Structure and efficient luminescence upconversion of Ln(iii) aromatic N-oxide coordination polymers

Contact Info

Product

Resources

About

Europium(III) Photoluminescence Governed by d⁸–d¹⁰ Heterometallophilic Interactions in Trimetallic Cyanido-Bridged Coordination Frameworks