Relativistic DFT and experimental studies of mono- and bis-actinyl complexes of an expanded Schiff-base polypyrrole macrocycle

Zheng, Xiu-Jun; Bell, Nicola L.; Stevens, Charlotte J.; Zhong, Yu-Xi; Schreckenbach, Georg; Arnold, Polly L.; Love, Jason B.; Pan, Qing‐Jiang

doi:10.1039/c6dt01625a

Cited by 17 publications

(15 citation statements)

References 91 publications

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“…Coordination of an electropositive metal within the vacant compartment of the macrocycle was shown to activate the uranyl towards reduction so forming a range of stable mixed-metal, [U V O 2 ] + com-plexes. 10,11 The anthracenyl linker enforces both a greater distance between the N 4 -coordination compartments and a greater degree of coplanarity. Fe(II), Mn(II)) did not promote reduction and the corresponding uranyl(VI) U VI O 2 M(L Me ) complexes were isolated.…”

Section: Introductionmentioning

confidence: 99%

Controlling uranyl oxo group interactions to group 14 elements using polypyrrolic Schiff-base macrocyclic ligands

2016

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Heterodinuclear uranyl/group 14 complexes of the aryl- and anthracenyl-linked Schiff-base macrocyclic ligands L and L were synthesised by reaction of UO(HL) with M{N(SiMe)} (M = Ge, Sn, Pb). For complexes of the anthracenyl-linked ligand (L) the group 14 metal sits out of the N-donor plane by up to 0.7 Å resulting in relatively short MOUO distances which decrease down the group; however, the solid state structures and IR spectroscopic analyses suggest little interaction occurs between the oxo and group 14 metal. In contrast, the smaller aryl-linked ligand (L) enforces greater interaction between the metals; only the Pb complex was cleanly accessible although this complex was relatively unstable in the presence of HN(SiMe) and some organic oxidants. In this case, the equatorial coordination of pyridine-N-oxide causes a 0.08 Å elongation of the endo UO bond and a clear interaction of the uranyl ion with the Pb(ii) cation in the second donor compartment.

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Section: Introductionmentioning

confidence: 99%

Controlling uranyl oxo group interactions to group 14 elements using polypyrrolic Schiff-base macrocyclic ligands

2016

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“…And their formation reaction energetics was addressed, particularly for the uranyl complexes where the single pyridine coordinated [(py)(U VI O 2 ) 2 (L)] (B‐( s ‐ py)U VI ) and the pyridine‐free [(U VI O 2 ) 2 (L)] (B‐ U VI ) and [(U VI O 2 )(H 2 L)] (M‐ U VI ) were added for comparison. This work complements our recent work that focuses on the synthesis and characterization from experiment (for U) and the structural optimization from computation (U, Np, and Pu).…”

Section: Computational Detailsmentioning

confidence: 55%

“…Our previous theoretical study suggested that the penta valent uranyl bar is less rigid than the hexa valent one and more easily transformed to the cis ‐structure. Experimentally, Arnold and Love et al have chemically modified the aryl‐linked H 4 L Ar ligand and prepared an anthracenyl‐containing polypyrrolic macrocycle (H 4 L, Chart ) that has longer linker . The enlarged space allows the ligand H 4 L to complexate two trans ‐uranyl(VI) rods .…”

Section: Introductionmentioning

confidence: 99%

“…Experimentally, Arnold and Love et al have chemically modified the aryl‐linked H 4 L Ar ligand and prepared an anthracenyl‐containing polypyrrolic macrocycle (H 4 L, Chart ) that has longer linker . The enlarged space allows the ligand H 4 L to complexate two trans ‐uranyl(VI) rods . Recent development in the synthetic technique enables to control the metal number (monometallic uranyl, homo bimetallic uranyls as well as hetero bimetallic uranyl and main‐group metal like Ge, Sn, and Pb) in the formed complexes, and change the sort of solvent (pyridine and THF) that saturates the uranyl ion barring other four that is provided by the N 4 ‐donor compartment of the macrocycle .…”

Section: Introductionmentioning

confidence: 99%

“…The enlarged space allows the ligand H 4 L to complexate two trans ‐uranyl(VI) rods . Recent development in the synthetic technique enables to control the metal number (monometallic uranyl, homo bimetallic uranyls as well as hetero bimetallic uranyl and main‐group metal like Ge, Sn, and Pb) in the formed complexes, and change the sort of solvent (pyridine and THF) that saturates the uranyl ion barring other four that is provided by the N 4 ‐donor compartment of the macrocycle . However, analogous penta valent uranyl complex of H 4 L has not been synthesized.…”

Section: Introductionmentioning

confidence: 99%

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Infrared vibrational spectra, electronic structures, and formation reactions of polypyrrolic mono‐ and bis‐actinyl complexes: A relativistic DFT study

Zheng

Xuan

et al. 2017

Int J of Quantum Chemistry

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The development of synthetic techniques has enabled synthesis and characterization of a series of mono and bis-uranyl complexes of octadentate polypyrrolic macrocycles such as aryl-lined H 4 L Ar and anthracenyl-linked H 4 L, which is complemented by theoretical investigation via extending to more toxic and radioactive transuranics. The relativistic density functional theory (DFT) study has been dedicated to twelve actinyl complexes supported by the H 4 L ligand. The actinides include U, Np, and Pu elements, and either one or two is rendered in complexes with oxidation states of V or VI. Calculated symmetric/asymmetric An 5 O stretching vibrational frequencies show the decreasing trend along U, Np, and Pu, which is consistent with calculated bond orders. The hydrogen bonds between -yl endo-oxo and remaining hydrogen atoms of pyrrolides in mononuclear complexes cause pronounced redshift of An 5 O vibrational frequencies compared to those in binuclear complexes, so does the reduction from hexa-to pentavalent complexes. The electronic structures of actinyl complexes were calculated. For example, B-pyU VI possesses low-lying U(5f)character virtual orbitals, where f(d) and f(/) orbitals occur in low-energy region and p-type ones are residing further high; the r*(U 5 O) and r(U 5 O) orbitals are significantly split over 7 eV. The previous experimental observation that the 1:1 reactions between uranyl salts and the macrocycle tend to give a mixture of bis-and mono-uranyl complexes, with bis-the major product, has been corroborated by computational studies of the thermodynamics of the reactions. K E Y W O R D S electronic structure, polypyrrolic actinyl complexes, relativistic DFT, thermodynamic energy, vibrational spectra | I N T R O D U C T I O NIn addition to the utilization in the separation science, [1][2][3][4][5] nitrogendonor ligands such as polypyrrolic macrocycle, 2,6-bis(trazinyl)pyridine and their derivatives have greatly excited the coordination chemistry of actinides. [6][7][8][9][10][11][12][13][14][15][16][17] A flexible octadentate polypyrrolic ligand (H 4 L Ar ), [18,19] for instance, is versatile, because it can accommodate diverse metal ions ranging from actinide (An), lanthanide (Ln) to transition metal, different metal ion number, and various metal oxidation (eg, III-VI for uranium). [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35][36] Most of actinide-containing complexes supported by the H 4 L Ar ligand adopt the intriguing "Pacman-like" structure, in contrast to a recently synthesized nonclassic one. [36] The obtained bis-uranyl polypyrrolic complexes, [(ROU V (l-O)) 2 (L Ar )] (R 5 i Pr, SiMe 3 , SnPh 3 , Sn n Bu 3 , and Lipy 3 ), [28][29][30] show one cis-uranyl and one trans-one that are bonded by the cation-cation interaction (CCI) [37][38][39][40][41][42] . It is worth noting that one uranyl unit, usually retaining linear, has to be bent to suit the small space inside the mouth of these "Pacman-like" complexes. No hexavalent bis-uranyl counterpart has been found so far. Our p...

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Pacman‐Like Alkaliated Actinyl Complexes of a Polypyrrolic Macrocycle: A Relativistic DFT Study

Zhong

Zhou

et al. 2017

ChemistrySelect

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A series of doubly alkaliated actinyl complexes, [(thf)(An m O 2 )(A 2 L)] n-(An m -A; An= U, Np and Pu; m = VI and n = 0; m = V and n = 1; A = Li, Na and K; L is an octadentate polypyrrolic tetraanion) have been investigated for their structures, transformation reaction energies and redox property using relativistic density functional theory. The study confirms experimental results of the synthesized lithiated uranyl complexes and the proposed potassiated uranyl ones, and furthermore extends to more toxic and radioactive transuranics that are difficultly handled in experiment. Comparison with hydrogen analogues, [(thf)(An m O 2 )(H 2 L)] n-(An m -H), finds that the introduction of alkali atoms lengthens An=O endo and An=O exo bonds. Transformation reaction of An m -A (A = Li, Na and K) starting from the respective An m -H was calculated to be exothermic. The alkaliated complex shows more positive reduction potential in most cases. All the results unravel the alkali-mediated activation on the inert uranyl(VI) U=O bonding; the lithium complex, for instance, possesses the largest reduction potential (E 0 corr ), which indicates the strongest lithium activation. Further comparison was also made with the alkaliated uranyl complexes where the alkali metals are saturated by thf molecules.[a] Prof.

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Relativistic DFT and experimental studies of mono- and bis-actinyl complexes of an expanded Schiff-base polypyrrole macrocycle

Cited by 17 publications

References 91 publications

Controlling uranyl oxo group interactions to group 14 elements using polypyrrolic Schiff-base macrocyclic ligands

Controlling uranyl oxo group interactions to group 14 elements using polypyrrolic Schiff-base macrocyclic ligands

Infrared vibrational spectra, electronic structures, and formation reactions of polypyrrolic mono‐ and bis‐actinyl complexes: A relativistic DFT study

Pacman‐Like Alkaliated Actinyl Complexes of a Polypyrrolic Macrocycle: A Relativistic DFT Study

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