Three new bismuth(III) pyridine-2,6-dicarboxylate compounds: Synthesis, characterization and crystal structures

Hakimi, Mohammad; Motieiyan, Elham; Bertolotti, Federica; Marabello, Domenica; Rodrigues, V. H.

doi:10.1016/j.molstruc.2015.06.084

Cited by 15 publications

(10 citation statements)

References 54 publications

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“…The bond distances of five Bi–O and three Bi–N are 2.362(2)–2.577(2) and 2.493(3)–2.609(3) Å, respectively (see Table S6). The observed Bi–O/N distances are comparable to those of the related Bi(III) complexes containing 2,6-pdc ligands. ,, Bi 3+ cation exhibits a highly distorted BiO 5 N 3 polyhedron with the coordinated ligands owing to the lone pair. The oxidation state of Bi 3+ cation can be confirmed by the calculated BVS value of 3.18. − The C–N and C–O distances in the three linkers are 1.318(5)–1.343(4) and 1.220(5)–1.308(5) Å, respectively.…”

Section: Resultssupporting

confidence: 60%

Second-Harmonic Generation and Photoluminescence Properties of Sn(II)- and Bi(III)-Based Lone Pair Cation–Pyridine Dicarboxylate Coordination Compounds

Chen

et al. 2020

Inorg. Chem.

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Lone pair cation-based novel coordination compounds Sn[(pdc)(H2O)] (Sn–I) and (H2bpy)[Bi(pdc)2(Hpdc)]·5H2O (Bi–I) (pdc = pyridine-2,6-dicarboxylate; bpy = 4,4′-bipyridine) were synthesized through mild hydrothermal reactions. While Sn–I crystallizing in the polar space group, Pca21, exhibits a helical chain structure consisting of SnO3N distorted seesaws, 2,6-pdc linkers, and water molecules, Bi–I crystallizing in the centrosymmetric (CS) space group, P1̅, reveals a pseudo-3D network composed of BiO5N3 polyhedra, 2,6-pdc ligands, H2bpy2+ cations, and isolated H2O molecules. The lone cations Sn2+ and Bi3+ in the title compounds are in a highly deformed polyhedral environment. The single-crystal-to-single-crystal transformation from Sn–I to the anhydrous Sn[(pdc)] (Sn–II) with the polar noncentrosymmetric structure was successfully achieved upon heating crystals of Sn–I. UV–vis diffuse reflectance spectra indicate that the introduction of Sn2+ or Bi3+ red-shifts the adsorption edges upon coordination. Powder second-harmonic generation (SHG) measurements indicate that Sn–I and Sn–II are type-I phase-matchable and exhibit SHG intensity of ca. 15 and 35 times that of α-SiO2, respectively. Solid state photoluminescence (PL) measurements indicate that Bi–I is an excellent green emitting phosphor with the quantum efficiency up to 26% and outstanding decay lifetime of 1.82 ms at room temperature.

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Section: Resultssupporting

confidence: 60%

Second-Harmonic Generation and Photoluminescence Properties of Sn(II)- and Bi(III)-Based Lone Pair Cation–Pyridine Dicarboxylate Coordination Compounds

Chen

et al. 2020

Inorg. Chem.

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“…In an effort to provide further insight into the structure–property relationships that underpin the photophysical behavior of Bi-based materials, in this work the synthesis and luminescent properties of a bismuth–organic compound, consisting of 2,6-pyridinedicarboxylate (PDC) and 1,10-phenanthroline (phen), was examined. Dimeric complexes are well established in Bi-PDC systems, − with hydrogen-bond acceptors often bound perpendicularly to the plane of PDC. We hypothesized that these subunits would provide suitable structural units with which the photophysical behavior of a rigid, otherwise weakly emissive compound (Hphen) could be explored.…”

Section: Introductionmentioning

confidence: 99%

Harnessing Bismuth Coordination Chemistry to Achieve Bright, Long-Lived Organic Phosphorescence

et al. 2021

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A new bismuth(III)−organic compound, Hphen-[Bi 2 (HPDC) 2 (PDC) 2 (NO 3 )]•4H 2 O (Bi-1; PDC = 2,6-pyridinedicarboxylate and phen = 1,10-phenanthroline), was synthesized, and the structure was determined by single-crystal X-ray diffraction. The compound was found to display bright-bluegreen phosphorescence in the solid state under UV irradiation, with a luminescent lifetime of 1.776 ms at room temperature. The room temperature and low-temperature (77 K) emission spectra exhibited the vibronic structure characteristic of Hphen phosphorescence. Time-dependent density functional theory studies showed that the excitation pathway arises from an energy transfer from the dimeric structural unit to Hphen, with participation from a ninecoordinate Bi center. The triplet state of Hphen is believed to be stabilized via supramolecular interactions, which, when coupled with the heavy-atom effect induced by Bi, leads to the observed longlived luminescence. The compound displayed a solid-state quantum yield of over 27%. To the best of our knowledge, this is the first such compound to exhibit phenanthrolinium phosphorescence with such long-lived, room temperature lifetimes in the solid state. To further elucidate the energy-transfer mechanism, Ln 3+ (Ln = Eu, Tb, Sm) ions were successfully doped into the parent compound, and the resulting materials exhibited dual emission from Hphen and Ln, promoting tunability of the emission color.

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“…From the breadth of these compounds currently in literature, a strong propensity is seen for the formation of dimers or polymeric networks,[5f], [10c], with few examples showing monomeric Bi III centers. [13d] Discrete bismuth(III) oxo clusters, including 9‐, 10‐, 12‐, and 38‐nuclear clusters[9b], have been prepared. Until recently, the vast majority of these studies have focused on benzoate‐based ligands, yet the use of other heterocycles remains largely absent.…”

Section: Resultsmentioning

confidence: 99%

“…[2d], , [12a] In addition, pyridine mono‐ and dicarboxylate–bismuth compounds have been of significant interest, adopting mononuclear and dinuclear molecular complexes, 1D chains, 2D sheets, and 3D supramolecular networks. [5d], Such compounds exhibit interesting catalytic activity, potential semiconductor properties, and photoluminescent behavior …”

Section: Introductionmentioning

confidence: 99%

Structural Diversity of Bismuth(III) Thiophenemonocarboxylates Isolated from Aqueous Solutions

et al. 2017

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Five novel BiIII–thiophenemonocarboxylate (BiIII–TMC) compounds containing pyridinium cations have been synthesized from room‐temperature reactions of bismuth precursors with 2‐thiophenecarboxylic acid (HTMC) and pyridine in water. The structures have been determined by single‐crystal X‐ray diffraction, and two of the compounds have been further characterized by Raman spectroscopy and thermogravimetric analysis. The solid‐state structures of the compounds are built from anionic BiIII building units that vary in nuclearity, overall connectivity, and dimensionality. When using bismuth nitrate at a relatively low metal/ligand ratio, Hpy[Bi(TMC)4(HTMC)] (1) is formed, which consists of mononuclear units charge‐balanced by second coordination sphere pyridinium cations. With increasing metal/ligand ratios, and by consequence, increasing nitrate concentration, nitrate and carboxylate‐bridged chains of [Bi2(TMC)3(NO3)]– units in Hpy[Bi2(TMC)6(NO3)] (2), and nitrate‐bridged [Bi2(TMC)3(NO3)2]2– dimers in Hpy[Bi(TMC)3(NO3)] (3) are isolated. Starting from Bi2O3, polymorphs (Hpy)2[Bi2(TMC)8] (4) and (Hpy)2[Bi2(TMC)8] (5) are formed, both of which contain bismuth centers bridged by carboxylate groups to form dimeric units that are charge‐balanced by pyridinium cations. Presented herein is a discussion of the synthetic conditions over which 1–5 were isolated, and their solid‐state structural chemistry. The thermal stability of 1 and 3, and the spectroscopic characterization of the compounds, are also reported.

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Three new bismuth(III) pyridine-2,6-dicarboxylate compounds: Synthesis, characterization and crystal structures

Cited by 15 publications

References 54 publications

Second-Harmonic Generation and Photoluminescence Properties of Sn(II)- and Bi(III)-Based Lone Pair Cation–Pyridine Dicarboxylate Coordination Compounds

Second-Harmonic Generation and Photoluminescence Properties of Sn(II)- and Bi(III)-Based Lone Pair Cation–Pyridine Dicarboxylate Coordination Compounds

Harnessing Bismuth Coordination Chemistry to Achieve Bright, Long-Lived Organic Phosphorescence

Structural Diversity of Bismuth(III) Thiophenemonocarboxylates Isolated from Aqueous Solutions

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