Theoretical investigation on the ground state properties of the hexaamminecobalt(<scp>iii</scp>) and nitro–nitrito linkage isomerism in pentaamminecobalt(<scp>iii</scp>) <i>in vacuo</i>

Muya, Jules Tshishimbi; Chung, Hoeil; Lee, Sang Uck

doi:10.1039/c7ra11603a

Cited by 14 publications

(32 citation statements)

References 76 publications

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“…The single point energies difference between the experimental geometries of A and B computed at HF/LanL2DZ shows A to be 20.32 kcal/mol more stable than B , while M062X/6‐31+G(d,p) geometry optimization reveals that A lies 10 and 0.15 kcal/mol (25.98 and 11.90 kcal/mol at B3LYP‐D3/6‐31+G(d,p)) below B and the endo ‐form. Hence, this endo ‐form appears to be a possible viable intermediate structure in solid state upon linkage isomerization process …”

Section: Resultsmentioning

confidence: 97%

“…Thus, IHBs tend to be stronger in [Co(NH 3 ) 5 NO 2 ]Cl + than in [Co(NH 3 ) 5 ONO]Cl + . According to Muya et al, the difference in IHB in [Co(NH 3 ) 5 NO 2 ] 2+ linkage isomers can be explained by the decrease of electron resonance in the nitrito group compared to the nitro group. Another way to probe the strength of hydrogen bonds in those complexes is to determine the bond lengths of the NH bonds in the ammonia ligands.…”

Section: Resultsmentioning

confidence: 99%

“…The endo ‐[Co(NH 3 ) 5 ONO](NO 3 )Cl can be suspected as a possible intermediate, but has not yet been captured and stabilized experimentally. Muya et al suggested that the nitrito/ exo ‐nitrito isomerization reaction occurs via the [Co(NH 3 ) 5 NO 2 ] 2+ → [Co(NH 3 ) 5 NO 2 ] 2+ (TS1) → [ endo ‐Co(NH 3 ) 5 ONO] 2+ → [Co(NH 3 ) 5 NO 2 ] 2+ (TS2) → [ exo ‐Co(NH 3 ) 5 ONO] 2+ reaction pathway. The transformation of [Co(NH 3 ) 5 NO 2 ] 2+ into [ endo ‐Co(NH 3 ) 5 ONO] 2+ was found to be thermodynamically controlled whereas that of [ endo ‐Co(NH 3 ) 5 ONO] 2+ to [ exo ‐Co(NH 3 ) 5 ONO] 2+ was reported to be kinetically controlled.…”

Section: Resultsmentioning

confidence: 99%

“…The previous studies suggestion that the endo ‐[Co(NH 3 ) 5 ONO] 2+ isomer may be an intermediate species in the nitro/nitrito isomerization motivated our present study; we assumed that the endohedral orientation of the nitrito group in [Co(NH 3 ) 5 ONO](NO 3 )Cl enables more hydrogen bonds to form between O and the H of ammonia in the equatorial region, bringing extra stability to the complex. Furthermore, the orientation of chloride and nitrate anions in [Co(NH 3 ) 5 NO 2 ](NO 3 )Cl and [Co(NH 3 ) 5 ONO](NO 3 )Cl is also examined and compared with their positions reported in A and B crystals .…”

Section: Introductionmentioning

confidence: 90%

“…nitro ➔ TS1 (38.16 kcal/mol) ➔ endo ‐nitrito ➔ TS2 (9.68 kcal/mol) ➔ exo ‐nitrito) was found to be the most likely mechanism. The endo ‐[Co(NH 3 ) 5 ONO] 2+ isomer (with ONO in the endohedral orientation) was found to be slightly more stable than its counterpart exo ‐[Co(NH 3 ) 5 ONO] 2+ isomer (with ONO in the exohedral orientation) . There has been continuing interest in the study of [Co(NH 3 ) 5 NO 2 ](NO 3 )Cl isomers due to their potential applications in stimuli‐responsive materials, energy harvesting, tunable contact printing, artificial muscles, mechanically tunable optical elements, and switchable reflector elements for projective displays .…”

Section: Introductionmentioning

confidence: 99%

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A theoretical insight into the role of counter anions and their interactions in nitropentaamminecobalt(III) toward linkage isomerism‐induced photochemical motion

Muya

Meher

Sahoo

et al. 2019

Int J of Quantum Chemistry

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Density functional theory (B3LYP, B3LYP‐D3, wB97XD, M062X, and M06L) and ab initio methods (MP2 and CCSD(T)) in conjunction with 6‐31+G(d,p) and LanL2DZ were employed to investigate the interaction energies between [Co(NH3)5NO2]2+ linkage isomers and chloride and nitrate in both gas phase and solid state. The nature of the chemical bonding has been analyzed by means of the atoms in molecules, electron density shift, natural bond orbitals, symmetry adapted perturbation theory, and energy decomposition analysis. The electronic structures of the two lowest laying singlet states (So and S1) of [Co(NH3)5NO2](NO3)Cl isomers were also investigated using CASSCF(6,6) with LanL2DZ and 6‐31G(d) basis sets. Our results show that [Co(NH3)5NO2]2+ linkage isomers interact more strongly with chloride than nitrate. The structures of [Co(NH3)5NO2](NO3)Cl linkage isomers and their relative stabilities were examined in gas phase and in solid state and confirmed the nitro‐complex as the most stable following by a viable intermediate endo‐complex. Study of the nitro‐nitrito linkage isomerization in [Co(NH3)5NO2](NO3)Cl revealed that anions form strong electrostatic bonds with [Co(NH3)5NO2]2+ leading to decrease in an activation energy compared to the [Co(NH3)5ONO]2+ isomers. A concerted action of ionic interactions and hydrogen bonds are suspected of regulating the isomerization in solid state. Assessment of various DFT methods with respect to CCSD(T) suggests M062X suitable method for [Co(NH3)5NO2](NO3)Cl linkage‐isomerization study. Potential energy surface calculations at the CASSCF/6‐31G(d) level of theory shows that the conical intersection (S1/So) might play an important role in the photoisomerization of [Co(NH3)5NO2](NO3)Cl.

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Section: Resultsmentioning

confidence: 97%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 90%

Section: Introductionmentioning

confidence: 99%

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A theoretical insight into the role of counter anions and their interactions in nitropentaamminecobalt(III) toward linkage isomerism‐induced photochemical motion

Muya

Meher

Sahoo

et al. 2019

Int J of Quantum Chemistry

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Interrelations between Linkage Isomers of an Efficient Square‐planar Nickel(II) Nitrite Photoswitch in the Solid State

Potempa,

Deresz,

Jankowska

et al. 2023

Chemistry A European J

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An efficient nitrite nickel(II) photoswitch, with the 1‐phenyl‐2‐hydroxyimino‐3‐[(2’‐dimethylamino)ethyl]imino‐1‐propanone moiety used as the ancillary ligand, is reported. In the ground‐state (‘dark’) crystal structure, the studied compound exists predominantly as the nitro‐(η1‐N(O)2) isomer, however, traces of the exo‐ and endo‐nitrito‐(η1‐ONO) forms are detected both at 100 K (4−5% each) and under ambient conditions (~9% each). When excited with the 405−530 nm LED light, the nitro‐to‐nitrito isomerization takes place. The total conversion exceeds 90%. The exo‐nitrito linkage isomer constitutes the dominant photo‐generated form, whereas the relative population of both nitrito species depends on temperature. The reaction is fully reversible and reproducible. The photo‐products are stable up to 200 K. The system constitutes a good model case for the reaction mechanism studies. Thus, experimental and theoretical investigations on the photo‐isomerism were conducted and are presented in detail. Eventually, the nitro → exo‐nitrito → endo‐nitrito reaction pathway is proposed.

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Excellent photo actuation in crystal-polymer composite by transfer of mechanical energy

Singh

Abhijitha

Nanda

et al. 2023

Chemical Engineering Journal

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Theoretical investigation on the ground state properties of the hexaamminecobalt(iii) and nitro–nitrito linkage isomerism in pentaamminecobalt(iii) in vacuo

Abstract: Nitro–nitrito isomerization in Co(NH3)5NO22+ linkage isomers was investigated with a focus on the geometries, relative stabilities and chemical bonding using ωB97XD/6-31+G(d,p) to elucidate the photo-salient effect in [Co(NH3)5NO2]NO3Cl.

Cited by 14 publications

References 76 publications

A theoretical insight into the role of counter anions and their interactions in nitropentaamminecobalt(III) toward linkage isomerism‐induced photochemical motion

A theoretical insight into the role of counter anions and their interactions in nitropentaamminecobalt(III) toward linkage isomerism‐induced photochemical motion

Interrelations between Linkage Isomers of an Efficient Square‐planar Nickel(II) Nitrite Photoswitch in the Solid State

Excellent photo actuation in crystal-polymer composite by transfer of mechanical energy

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