Pb–Oxo Interactions in Uranyl Hybrid Materials: A Combined Experimental and Computational Analysis of Bonding and Spectroscopic Properties

The new cyanido-bridged mixed valent FeII/CoIII macrocyclic complexes [L2CoIII(μ-NC)FeII(CN)5]– and trans-[L2CoIII(μ-NC)FeII(CN)4(μ-CN)CoIIIL2]2+ have been prepared and characterized spectroscopically. The trinuclear complex trans-[L2Co(μ-NC)Fe(CN)4(μ-CN)CoL2](ClO4)2·11H2O has been characterized crystallographically. The di- and trinuclear complexes exhibit metal-to-metal charge transfer transitions characteristic of Class II mixed valent chromophores and their redox and spectroscopic properties have been analyzed by Hush theory. The thiophene group attached to the macrocycle L2 in these complexes may serve as a precursor to conducting polythiophene-based hybrid materials incorporating redox active transition metal ions.

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Exploration of supramolecular interactions in a series of UO22+hybrid materials

Acta Crystallographica Section A Foundations and Advances ◽

10.1107/s2053273314093589 ◽

2014 ◽

Vol 70 (a1) ◽

pp. C641-C641

Author(s):

Korey Carter ◽

Sonia Thangavelu ◽

Christopher Cahill

Keyword(s):

Solid State ◽

Benzoic Acid ◽

Hybrid Materials ◽

Spectroscopic Properties ◽

Acid Group ◽

Supramolecular Interactions ◽

Donor Ligands ◽

X Ray Diffraction ◽

Metal Centers ◽

Influence Of Ph

Previous work from our group has focused on uranyl hybrid materials with para-substituted halogen benzoic acids.1 Applying a `cap and link' strategy we have successfully controlled the nuclearity of UO22+ in a series of coordination polymers and Ln3+ in a family of molecular materials.2,3 Here we have expanded on this strategy and produced a series of 12 unique uranyl hybrid materials. The hydrothermally synthesized complexes all feature bromo-substituted benzoic acid linkers and the UO22+ metal centers are capped with a chelating N-donor. Single crystal X-ray diffraction analyses of these materials allowed for the exploration of the structural relationship between the benzoic acid group and the chelating N-donor as well as the influence of pH on uranyl speciation. At an unadjusted pH (~3) a mix of molecular monomers and dimers are observed while at higher pH (5-6) molecular uranyl dimers are exclusively produced. A systematic study of the supramolecular interactions that governed extended solid-state assembly was investigated by varying the bromine position on the benzoic acid groups along with the chelating N-donor with pH. Assembly via halogen-halogen, halogen-π, π-π, and halogen-oxygen interactions was observed and the influence of these interactions on uranyl emission was also investigated. Solid-state luminescence and lifetime measurements were used to explore the effects of speciation and chelating N-donor ligands on the spectroscopic properties of the uranyl cation.

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Assessing electronic properties of desymmetrized heterocyclic patterns: towards tuning small molecules for photovoltaic applications

MRS Advances ◽

10.1557/adv.2020.434 ◽

2020 ◽

Vol 5 (61) ◽

pp. 3171-3184

Author(s):

Oscar González-Antonio ◽

Rebeca Yépez ◽

María Magdalena Vázquez-Alvarado ◽

Blas Flores-Pérez ◽

Norberto Farfán ◽

...

Keyword(s):

Small Molecules ◽

Heterocyclic Compounds ◽

Computational Analysis ◽

Organic Molecules ◽

Spectroscopic Properties ◽

Small Organic Molecules ◽

Photovoltaic Materials ◽

Photovoltaic Applications ◽

Donor Acceptor ◽

Homo Lumo

AbstractA series of highly attainable desymmetrized heterocyclic compounds with Donor-Acceptor-Donor-Acceptor-X (D-A-D-X) architectures were synthesized. The structures, where X corresponds to a heteroaromatic portion (pyridine, ferrocene, thiadiazolopyridine), were designed through computational analysis. Molecular geometries for all compounds were studied and parameters of charge transfer were computed in order to analyse the behaviour in each architecture. Spectroscopic properties (maximum absorption wavelengths, extinction coefficients and HOMO-LUMO gaps) were predicted and measured experimentally. UV-Vis absorption profiles and values of HOMO-LUMO optical gaps (in the vicinity of 2.0 eV), together with the computational results, are properties that position the obtained systems, as potential candidates for developing efficient photovoltaic materials based on synthetically accessible small organic molecules.

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Computational analysis of vibrational spectroscopic properties and hyperpolarizability of silver adsorbed organic molecule, N,N’ Dimethyl Urea Ninhydrin

Spectrochimica Acta Part A Molecular and Biomolecular Spectroscopy ◽

10.1016/j.saa.2019.117698 ◽

2020 ◽

Vol 228 ◽

pp. 117698

Author(s):

Jerin Susan John ◽

D. Sajan

Keyword(s):

Organic Molecule ◽

Computational Analysis ◽

Spectroscopic Properties ◽

Dimethyl Urea

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The influence of pH over topography and spectroscopic properties of silica hybrid materials embedding meso-tetratolylporphyrin

Materials Research Bulletin ◽

10.1016/j.materresbull.2008.04.023 ◽

2009 ◽

Vol 44 (2) ◽

pp. 426-431 ◽

Cited By ~ 14

Author(s):

Eugenia Fagadar-Cosma ◽

Corina Enache ◽

Ileana Armeanu ◽

Dana Dascalu ◽

Gheorghe Fagadar-Cosma ◽

...

Keyword(s):

Hybrid Materials ◽

Spectroscopic Properties ◽

Influence Of Ph ◽

Silica Hybrid

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Recent Advances in Crystalline Oxidopolyborate Complexes of d-Block or p-Block Metals: Structural Aspects, Syntheses, and Physical Properties

Molecules ◽

10.3390/molecules26133815 ◽

2021 ◽

Vol 26 (13) ◽

pp. 3815

Author(s):

Shu-Sheng Xin ◽

Ming-Hua Zhou ◽

Michael A. Beckett ◽

Chun-Yang Pan

Keyword(s):

Physical Properties ◽

Hybrid Materials ◽

Building Blocks ◽

Spectroscopic Properties ◽

Organic Metal ◽

Metal Centers ◽

Crystalline Materials ◽

Potential Applications ◽

Synthetic Approaches ◽

Structural Aspects

Crystalline materials containing hybrid inorganic–organic metal borates (complexes with oxidoborate ligands) display a variety of novel framework building blocks. The structural aspects of these hybrid metallaoxidoborates containing Cd(II), Co(II), Cu(II), Ga(III), In(III), Mn(II), Ni(II) or Zn(II) metal centers are discussed in this review. The review describes synthetic approaches to these hybrid materials, their physical properties, their spectroscopic properties and their potential applications.

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