Experimental and experimental-theoretical topological characteristics of the electron density distribution in the crystal of NCN-(2-pyridinecarbonitrile)-(3,6-di-tert-butylcatecholato)triphenylantimony(v)

Fukin, Georgy K.; Баранов, Е. В.; Cherkasov, Anton V.; Rumyantcev, Roman V.; Kozlova, Ekaterina A.; Okhlopkova, L. S.; Poddel’sky, Andrey I.

doi:10.1007/s11172-019-2607-z

Cited by 7 publications

(4 citation statements)

References 37 publications

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“…Therefore, it is fundamentally important to study the topology of electron density in order to evaluate the energy of the Rh–Rh interactions in the dimer and between them. Application of molecular invariom model allows us to get the distribution of electron density in the crystal without high-resolution X-ray diffraction experiments. , The literature review showed that the main topological characteristics obtained using the molecular invariom are in good agreement with density functional theory calculations and experimental data. − The molecular invarioms were calculated at a temperature of 298 and 110 K for complexes 1 ( 1 298 , 1 110 ) and 298 and 100 K for 2 ( 2 298 , 2 100 ) (Table S3). According to the quantum theory of atoms in molecules, interactions in the coordination sphere of the rhodium atoms in 1 and 2 are intermediate ones [covalent polar bond, ∇ 2 ρ( r ) > 0, h e ( r ) < 0] with the exception of the Rh–Rh interactions in the dimer and the Rh···Rh interactions between the dimers.…”

Section: Resultsmentioning

confidence: 86%

Single Crystal X-ray Diffraction Studies of Two Polymorphic Modifications of the Dicarbonyl-o-Semiquinonato Rhodium Complex at Different Temperatures. Destruction Stimulated by Cooling Versus Stability

et al. 2020

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It was found that the dicarbonyl-rhodium- o -semiquinonate complex (which thread-like crystals can bend reversibly under light/warm activation) can form two polymorphic modifications: isometric prisms ( 1 ) and sticks ( 2 ). Some thin sticks can bend as mentioned above. X-ray diffraction studies of polymorphic modifications at different temperatures were carried out. It was found that crystals 1 are destructed after cooling to 110 K as opposed to crystals 2 . In turn, the reversible phase transition is detected in 2 . In both polymorphic modifications, stack packaging motifs through the direct Rh–Rh bond are observed. The principal difference between packages of polymorphic modifications is that molecules 1 in the adjacent stacks are shifted relative to each other along the stack, in contrast to crystal 2 . It was found that different packing of stacks leads to different anisotropic compression of crystals 1 and 2 during cooling, which is a key factor of their stability. Using the molecular invariom approach, the nature of the chemical bonds and charge distribution was investigated; the energy of the Rh–Rh bonds was estimated.

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Section: Resultsmentioning

confidence: 86%

Single Crystal X-ray Diffraction Studies of Two Polymorphic Modifications of the Dicarbonyl-o-Semiquinonato Rhodium Complex at Different Temperatures. Destruction Stimulated by Cooling Versus Stability

et al. 2020

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“…The use of this method provides an information about the topology of the ED in molecules with good accuracy [13,14]. However, the majority of studies in this area is devoted to the transferability of the topological characteristics in the coordination sphere of the metal atom [15][16][17].…”

Section: Introductionmentioning

confidence: 99%

Application of the Molecular Invariom Model for the Study of Interactions Involving Fluorine Atoms in the {$${\text{Yb}}_{{\text{2}}}^{{{\text{II}}}}$$(μ2-OCH(CF3)2)3(μ3-OCH(CF3)2)2YbIII(OCH(CF3)2)2(THF)(Et2O)} Complex

et al. 2021

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The electron density distributions obtained by the quantum-chemical (density functional theory) calculations and molecular invariom model in the trimeric ytterbium complex with the hexafluoroisopropoxide ligands {$${\text{Yb}}_{{\text{2}}}^{{{\text{II}}}}$$(μ2-OR)3(μ3-OR)2YbIII(OR)2(THF)(Et2O)} (I) (where R is CH(CF3)2, and THF is tetrahydrofuran) are compared. The main topological characteristics of the electron density at the critical points (3, –1) corresponding to the interactions of the ytterbium atoms in the coordination sphere obtained using two studied approaches demonstrate excellent agreement. The maximum divergence between the density functional calculations and molecular invariom model is observed for the intramolecular interactions involving the fluorine atoms (F···F, F···H, and F···O) in the structure of complex I. Geometry optimization leads to a higher number of these interactions in the complex. The energy corresponding to these interactions also increases. However, the main topological characteristics for the F···X interactions (X = F, H, O), which can be localized in the framework of both methods, remain within the transferability index range. An analysis of the deformation electron density shows that the Fδ–···Fδ– interactions are determined by the correspondence of the region of electron density concentration on one of the fluorine atoms to the region of electron density depletion on the second fluorine atom regardless of the method of measuring the electron density distribution.

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“…Therefore, the concept of invarioms was further developed by introducing the whole-molecule aspherical scattering factor . This approach is called the “molecular invariom model”. − It has shown good reproducibility between the experimental and calculated DFT data for complexes of s, p, and d , elements. We used this access to investigate the electron density topologies in the lanthanide complexes 1 and 2 .…”

Section: Resultsmentioning

confidence: 99%

“…31 This approach is called the "molecular invariom model". 32−35 It has shown good reproducibility between the experimental and calculated DFT data for complexes of s, 36 p, 37 and d 38,39 elements. We used this access to investigate the electron density topologies in the lanthanide complexes 1 and 2.…”

Section: ■ Introductionmentioning

confidence: 85%

Unexpected Findings in a Simple Metathesis Reaction of Europium and Ytterbium Diiodides with Perfluorinated Mercaptobenzothiazolates of Alkali Metals

et al. 2020

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In the search for new f–d luminescent complexes of Eu(II) and Yb(II) the metathesis reactions of diiodides of these metals with perfluorinated 2-mercaptobenzothiazolates of alkali metals were studied. It has been found that the reactions of LnI2(THF)2 (Ln = Eu, Yb) with K(mbtF) (mbtF = perfluorinated 2-mercaptobenzothiazolate anion) in DME result in the formation of the nonluminescent complexes Ln(mbtF)2(DME)2 and precipitation of KI in high yields. Single-crystal X-ray diffraction analyses have shown that Eu(mbtF)2(DME)2 has a trans orientation of mbtF ligands, while in the Yb(mbtF)2(DME)2 molecule the ligands occupy cis positions. The DFT calculations and estimations with the invariom model revealed that the complexes have a flexible coordination sphere of Ln2+ ions and a relatively low energy of Ln–mbtF binding. The reactions of the same diiodides with the lithium complex Li(mbtF) are reversible and proceed through the formation of intermediate complexes of unknown structure which have been isolated as noncrystalline solids. The europium product (solid and in DME solution) upon UV excitation exhibited bright luminescence with λ 510 nm. Data from time-resolved photoluminescence (PL) spectroscopy indicated the existence in the intermediate substance of two Eu2+ emission centers with different coordinating environments. Treatment of the solid intermediate product with toluene led to its dissociation onto Ln(mbtF)2(DME)2 and [LiI(DME)] n . The back-replacement of toluene with DME gives again the solutions from which the starting LnI2 and Li(mbtF)(DME) were precipitated by slow evaporation of the solvent. The reversibility of the processes has been confirmed by the reaction of nonluminescent Eu(mbtF)2(DME)2 with LiI in DME medium, which resulted in the same luminescent solution which gave a mixture of EuI2(DME)3 and Li(mbtF).

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Experimental and experimental-theoretical topological characteristics of the electron density distribution in the crystal of NCN-(2-pyridinecarbonitrile)-(3,6-di-tert-butylcatecholato)triphenylantimony(v)

Cited by 7 publications

References 37 publications

Single Crystal X-ray Diffraction Studies of Two Polymorphic Modifications of the Dicarbonyl-o-Semiquinonato Rhodium Complex at Different Temperatures. Destruction Stimulated by Cooling Versus Stability

Single Crystal X-ray Diffraction Studies of Two Polymorphic Modifications of the Dicarbonyl-o-Semiquinonato Rhodium Complex at Different Temperatures. Destruction Stimulated by Cooling Versus Stability

Application of the Molecular Invariom Model for the Study of Interactions Involving Fluorine Atoms in the {$${\text{Yb}}_{{\text{2}}}^{{{\text{II}}}}$$(μ2-OCH(CF3)2)3(μ3-OCH(CF3)2)2YbIII(OCH(CF3)2)2(THF)(Et2O)} Complex

Unexpected Findings in a Simple Metathesis Reaction of Europium and Ytterbium Diiodides with Perfluorinated Mercaptobenzothiazolates of Alkali Metals

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