A NANOSTRUCTURED POLYMORPH OF Μ-Oxobis(phthalocyaninatoiron(iii)) STUDIED BY ANGULAR AND ENERGY DISPERSIVE X-Ray DIFFRACTION

Matassa, Roberto; Ballirano, Paolo; Donzello, Maria Pia; Ercolani, Claudio; Sadun, Claudia; Caminiti, Ruggero

doi:10.1142/s1793292007000398

Cited by 5 publications

(3 citation statements)

References 14 publications

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“…In order to further elucidate the electronic structures of 1a and 1b and elaborate on the optical and magnetooptical properties of dimers 1a , 1b , and 2Py , we have conducted density functional theory (DFT) and time-dependent DFT (TDDFT) calculations on these compounds. The choice of the exchange-correlation functional (ECF) used in calculations is discussed in detail in the Supporting Information and is based on the requirements expected for phthalocyanine μ-oxo dimers and double-decker Pc 2 Ln and [Pc 2 Ln] − complexes. − For the 1a and 1b complexes, geometry optimizations with the HISSbPBE ECF suggest that the lowest energies correspond to the broken-symmetry calculations in which two s = 5/2 iron(III) centers are antiferromagnetically coupled via the μ-oxo bridging atom. The high-spin and open-shell calculations result in significantly higher-energy structures, which agrees well with the diamagnetism of 1a and 1b (Table S2).…”

Section: Resultsmentioning

confidence: 99%

Role of MCD and Mössbauer Spectroscopy in the Explanation of the Properties of a Highly Soluble (μ-Oxo)bis[tetra(tert-butyl)(phthalocyaninato)iron(III)] Complex, Its Pyridine Adduct, and Redox Forms Oxidized under Anaerobic Conditions in Non-Coordinating Solvents

et al. 2023

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Solid-state Mössbauer spectra of a highly soluble (μ-oxo)bis[tetra(tert-butyl)(phthalocyaninato)iron(III)] complex 1 ((Pc tBuFe)2O) consist of two doublets that represent bent geometry in μ-oxo(1) (1a, ΔE Q = 0.43 mm/s, T = 10 K) and linear geometry in μ-oxo(2) (1b, ΔE Q = 1.40 mm/s, T = 10 K) isomers with the ratio between two isomers depending on the purification method. Both isomers were found to be diamagnetic and transform entirely to the 1a isomer in solution. The room- and low-temperature magnetic circular dichroism (MCD) spectra of 1a μ-oxo(1) show one Faraday A- and one B-term between 670 and 720 nm, which correlate with the 690 nm band and 709 nm shoulder observed in the UV–vis spectrum of this compound. UV–vis and MCD spectra of 1a are almost independent of the temperature. Both 1a and 1b are diamagnetic between room temperature and 4 K. Electrochemical experiments show up to three oxidations and up to four reduction processes in 1a. Its oxidation under spectroelectrochemical or chemical (in the absence of oxygen-containing oxidants) conditions in non-coordinating solvents results in the formation of broad NIR bands around 1195 nm (first oxidation) and 1264 nm (second oxidation). The MCD spectra of the redox-active species show a Faraday B-term signal with negative amplitude in this region and are very different from those in the monomeric Pc tBu(1−)FeIIIX2 complexes 5X (X = Cl– or CF3CO2 –). The pyridine adduct of 1a ((PyPc tBuFe)2O; 2Py) is paramagnetic (μB = 2.19, g = 2.11, and J = −6.1 cm–1) and has a major peak at 627 nm of its UV–vis spectrum, which is associated with a MCD pseudo A-term. Density functional theory (DFT) and time-dependent DFT (TDDFT) calculations, along with the exciton coupling theory, were used to explain the unusually red-shifted intense transitions in 1a as well as the H-aggregate-like spectra of the pyridine adduct 2Py.

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Section: Resultsmentioning

confidence: 99%

Role of MCD and Mössbauer Spectroscopy in the Explanation of the Properties of a Highly Soluble (μ-Oxo)bis[tetra(tert-butyl)(phthalocyaninato)iron(III)] Complex, Its Pyridine Adduct, and Redox Forms Oxidized under Anaerobic Conditions in Non-Coordinating Solvents

et al. 2023

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“…To simplify the model description, the structural parameters are referred to the centers of mass of the single chain in Figure A, including the main structural parameters. ,, In the inset the complete single chain of all atoms is shown. The atomic Cartesian coordinates corresponding to the cis -Pt-DEBP and the trans -[Pt(PBu 3 ) 2 Cl] tail/head of the oligomer are available in the Supporting Information, Tables 2S and 3S.…”

Section: Resultsmentioning

confidence: 99%

Organometallic Oligomer Resolved by Radial Distribution Function of X-ray Diffraction Analysis

et al. 2010

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Platinum-organic oligomers are actively studied for their large physical and functional properties such as solubility, processability, color, luminescence, and optoelectronics related to the different metal groups and auxiliary coligands around the metal coordination spheres. Previous studies on nanotechnology devices have shown that the structural organization of handled metallopolymer generates several 2D or 3D nano-objects, but only based on trans polymorph chains. Here we report the first self-assembly of powder cis-Pt-DEBP oligomers that shows great self-assembling ability to form nanoscale supramolecular architectures. As a powder is obtained that shows a poor crystalline organization of the aggregates, the energy-dispersive X-ray diffraction is the nondestructive technique of choice to obtain short-range order structural parameters of a single nano-object by radial distribution function analysis. The supramolecular architecture of 8-units-long chains reveals a self-assembling organization of 18 chains exhibiting an overall linear inverted open square structure. The ensemble of oligomer chains form a parallelepiped shape with small internal square cavities of approximately 3.2 nm diameter capable of hosting smaller molecules, which opens up to all applications where sieving and sensing is important. This structural investigation of short-range order materials has provided a substantial additional impetus to the field by opening up the area of self-assembled supramolecular materials based on metallopolymers for technological applications.

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“…[15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31] 3) Dioxygen activation, oxygen atom transfer, and oxidative catalysis. [28][29][30][31] 4) Synthesis and investigation of the molecular and electronic structure of single-atom bridged homo-and heterobimetallic µ-oxodiiron(III) bisphthalocyaninates; [32][33][34][35][36][37][38][39][40][41][42][43] as well as µ-nitrido [44][45][46][47][48][49][50][51] and µ-carbido [52][53] complexes of general formula (L)M-X-M'(L') (X = O, N, C; L and L' phthalocyanine or porphyrin dianions) containing iron in high-valence states (Fe IV ).…”

Section: Research Activitymentioning

confidence: 99%

Dedication to Professor Claudio Ercolani on the Occasion of his 75th Birthday

Stuzhin¹

2011

MHC

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A NANOSTRUCTURED POLYMORPH OF Μ-Oxobis(phthalocyaninatoiron(iii)) STUDIED BY ANGULAR AND ENERGY DISPERSIVE X-Ray DIFFRACTION

Cited by 5 publications

References 14 publications

Role of MCD and Mössbauer Spectroscopy in the Explanation of the Properties of a Highly Soluble (μ-Oxo)bis[tetra(tert-butyl)(phthalocyaninato)iron(III)] Complex, Its Pyridine Adduct, and Redox Forms Oxidized under Anaerobic Conditions in Non-Coordinating Solvents

Role of MCD and Mössbauer Spectroscopy in the Explanation of the Properties of a Highly Soluble (μ-Oxo)bis[tetra(tert-butyl)(phthalocyaninato)iron(III)] Complex, Its Pyridine Adduct, and Redox Forms Oxidized under Anaerobic Conditions in Non-Coordinating Solvents

Organometallic Oligomer Resolved by Radial Distribution Function of X-ray Diffraction Analysis

Dedication to Professor Claudio Ercolani on the Occasion of his 75th Birthday

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