Synthesis, Structures, and Luminescent Properties of Uranyl Terpyridine Aromatic Carboxylate Coordination Polymers

Thangavelu, Sonia G.; Andrews, Michael B.; Pope, Simon J. A.; Cahill, Christopher L.

doi:10.1021/ic3024698

Cited by 76 publications

(99 citation statements)

References 51 publications

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“…58−61 Analogous studies of uranyl compounds, however, are complicated by the spectral overlap of the UO 2 2+ ligand-to-metal charge transfer (LMCT) bands and π−π* transitions within the ligands. 44 Despite this limitation, we have observed that one may influence UO 2 2+ emission via appropriate choice of O-donor dicarboxylates with an appropriately situated triplet state in a series of materials containing TPY (Cl-TPY) ligands. 44 In the current work, the luminescence of uranyl CPs containing BPY and TPPZ ligands and the O-donor linker thiophene 2,5-dicarboxylic acid (TDC) was studied in an attempt to explore the influence bulky substituents may have on UO 2 2+ emission.…”

Section: ■ Introductionmentioning

confidence: 99%

“…44 Despite this limitation, we have observed that one may influence UO 2 2+ emission via appropriate choice of O-donor dicarboxylates with an appropriately situated triplet state in a series of materials containing TPY (Cl-TPY) ligands. 44 In the current work, the luminescence of uranyl CPs containing BPY and TPPZ ligands and the O-donor linker thiophene 2,5-dicarboxylic acid (TDC) was studied in an attempt to explore the influence bulky substituents may have on UO 2 2+ emission. In the present contribution, we continue on our theme on the influence O-donor and N-donor ligands may have on both the structure and the luminescence of uranyl CPs.…”

Section: ■ Introductionmentioning

confidence: 99%

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Role of N-Donor Sterics on the Coordination Environment and Dimensionality of Uranyl Thiophenedicarboxylate Coordination Polymers

Thangavelu

Butcher

Cahill

2015

Crystal Growth & Design

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Thiophene 2,5-dicarboxylic acid (TDC) was reacted with uranyl acetate dihydrate and one (or none) of six N-donor chelating ligands (2,2′-bipyridine (BPY), 4,4′-dimethyl-2,2′-bipyridine (4-MeBPY), 5,5′-dimethyl-2,2′-bipyridine (5-MeBPY), 6,6′-dimethyl-2,2′-bipyridine (6-MeBPY), 4,4′,6,6′-tetramethyl-2,2′-bipyridine (4,6-MeBPY), and tetrakis(2-pyridyl)pyrazine (TPPZ) to result in the crystallization of seven uranyl coordination polymers, which were characterized by their crystal structures and luminescence properties. The seven coordination polymers, Na 2 [(UO 2 ) 2 (C 6 H 2 O 4 S) 3 ]· (7), consist of either uranyl hexagonal bipyramidal or pentagonal bipyramidal coordination geometries. In all structures, structural variations in the local and global structures of 1−7 are influenced by the positions (or number) of methyl groups or pyridyl rings on the N-donor species, thus resulting in a wide diversity of structures ranging from single chains, double chains, or 2-D sheets. Direct coordination of N-donor ligands to uranyl centers is observed in the chain structures of 2−4 using BPY, 4-MeBPY, and 5-MeBPY, whereas the N-donor species participate as guests (as either neutral or charge balancing species) in the chain and sheet structures of 5−7 using 6-MeBPY, 4,6-MeBPY, and TPPZ, respectively. Compound 1 is the only structure that does not contain any N-donor ligands and thus crystallizes as a 2-D interpenetrating sheet. The luminescent properties of 1−7 are influenced by the direct coordination or noncoordination of N-donor species to uranyl centers. Compounds 2−4 exhibit typical UO 2 2+ emission upon direct coordination of N-donors, but its absence is observed in 1, 5, 6, and 7, when N-donor species participate as guest molecules. These results suggest that direct coordination of N-donor ligands participate as chromophores, thus resulting in possible UO 2 2+ sensitization. The lack of emission in 1, 5, 6, and 7 may be explained by the extended conjugation of the TDC ligands within their structures. ■ INTRODUCTIONCoordination polymers (CPs) constructed from the uranyl cation (UO 2 2+ ) continue to remain attractive in the field of hybrid materials owing to their unique structural and luminescent properties. 1 The UO 2 2+ cation is a linear triatomic species that contains two axial oxygen atoms about the central uranium atom, the terminal nature of which promotes additional ligand coordination about the equatorial plane. 2 This results in three types of UO 2 2+ primary building units (PBUs) found as square, pentagonal, or hexagonal bipyramidal geometries. The uranyl cation may also undergo hydrolysis and subsequent condensation to form secondary building units (SBUs) in the form of dimers, trimers, or tetramers, etc. 3,4 UO 2 2+ hydrolysis under hydrothermal conditions is a dynamic process wherein multiple speciation products are present in a wide range of pH and concentration. 5−7 This, in turn, makes it challenging to predict or control the type of uranyl building unit that will ultimately be observed in the solid st...

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Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Role of N-Donor Sterics on the Coordination Environment and Dimensionality of Uranyl Thiophenedicarboxylate Coordination Polymers

Thangavelu

Butcher

Cahill

2015

Crystal Growth & Design

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“…Common ligands used in the construction of uranyl CPs include the hard O-donor dicarboxylates, [6][7][8][9][10][11] and phosphonates, [12][13][14][15][16] due to their affinity for uranyl centers. 23 Herein, we expand our family of uranyl CPs to include another N-donor chelating ligand, 2,4,6-tripyridyl-s-triazine (TPTZ), since together with TPY, has been shown to chelate to uranyl centers 24 and thus may be a good candidate to promote a specific BU. [17][18][19][20][21] The incorporation of a secondary metal center often imparts additional properties to the overall material as well, including tuned uranyl emission using a transition metal (Fe 2+ ) 19 or sensitization of a lanthanide (Sm 3+ ) by uranyl via energy transfer.…”

Section: Introductionmentioning

confidence: 99%

“…22 Whereas the diversity of uranyl SBUs has given rise to a rich family of materials, challenges remain in directing the syntheses of topologies of interest. 23 Despite this limitation, we have shown that energy transfer within TPY containing uranyl CPs may be explored by comparing appropriately situated triplet states of organic linkers to the energy level of the emissive UO 2 2+ cation. That said, we have had some recent success in preparing a family of materials containing a fixed (and reproducible) uranyl center via the combined use of both chelating and ditopic ligands.…”

Section: Introductionmentioning

confidence: 99%

“…For example, one may influence speciation during synthesis with a combination of temperature, concentration and/or pH, yet determining which BUs will ultimately manifest themselves in the solid state remains elusive. 23 Another area of interest with respect to luminescence is lifetimes. Our previous efforts have shown TPY to be an effective chelator that promotes formation of a non-hydrolyzed uranyl building unit which may be assembled through various bifunctional carboxylates.…”

Section: Introductionmentioning

confidence: 99%

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Synthetic, structural, and luminescence study of uranyl coordination polymers containing chelating terpyridine and trispyridyltriazine ligands

2015

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·2H 2 O (7) containing N-donor ligands 2,2′:6′,2″-terpyridine (TPY) and 2,4,6-tripyridyl s-triazine (TPTZ); and O-donor linkers thiophene 2,5-dicarboxylic acid (TDC) and X-1,4-benzene dicarboxylic acid (X-BDC, where X = Me, Cl, Br, I) were synthesized and characterized using single crystal X-ray diffraction (SC-XRD), powder X-ray diffraction (PXRD), and fluorescence spectroscopy. Each compound crystallizes as binuclear pseudo dimers containing a UO 2 2+ pentagonal bipyramidal primary building unit. Fluorescence spectra of 1-4, and 6-7show characteristic UO 2 2+ emission whereas 5 is non-emissive. Red shifts within the emission of 1-4 are noted as a function of N-donor ligands TPY and TPTZ whereas emission shifts are not observed in TPTZ bearing compounds (3, 4, 6, 7) containing different O-donor linkers. Luminescent lifetimes of 1-7 were obtained and fitted with either bi-exponential or tri-exponential components.CrystEngComm This journal is

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Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms

Carter

Kalaj

Surbella

et al. 2017

Chemistry A European J

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Engaging the nominally terminal oxo atoms of the linear uranyl (UO ) cation in non-covalent interactions represents both a significant challenge and opportunity within the field of actinide hybrid materials. An approach has been developed for promoting oxo atom participation in a range of non-covalent interactions, through judicious choice of electron donating equatorial ligands and appropriately polarizable halogen-donor atoms. As such, a family of uranyl hybrid materials was generated based on a combination of 2,5-dihalobenzoic acid and aromatic, chelating N-donor ligands. Delineation of criteria for oxo participation in halogen bonding interactions has been achieved by preparing materials containing 2,5-dichloro- (25diClBA) and 2,5-dibromobenzoic acid (25diBrBA) coupled with 2,2'-bipyridine (bipy) (1 and 2), 1,10-phenanthroline (phen) (3-5), 2,2':6',2''-terpyridine (terpy) (6-8), or 4'-chloro-2,2':6',2''-terpyridine (Cl-terpy) (9-10), which have been characterized through single crystal X-ray diffraction, Raman, Infrared (IR), and luminescence spectroscopy, as well as through density functional calculations of electrostatic potentials. Looking comprehensively, these results are compared with recently published analogues featuring 2,5-diiodobenzoic acid which indicate that although inclusion of a capping ligand in the uranyl first coordination sphere is important, it is the polarizability of the selected halogen atom that ultimately drives halogen bonding interactions with the uranyl oxo atoms.

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Synthesis, Structures, and Luminescent Properties of Uranyl Terpyridine Aromatic Carboxylate Coordination Polymers

Cited by 76 publications

References 51 publications

Role of N-Donor Sterics on the Coordination Environment and Dimensionality of Uranyl Thiophenedicarboxylate Coordination Polymers

Role of N-Donor Sterics on the Coordination Environment and Dimensionality of Uranyl Thiophenedicarboxylate Coordination Polymers

Synthetic, structural, and luminescence study of uranyl coordination polymers containing chelating terpyridine and trispyridyltriazine ligands

Engaging the Terminal: Promoting Halogen Bonding Interactions with Uranyl Oxo Atoms

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