Photoresponsive Molecular Switch to Control Chemical Fixation of CO<sub>2</sub>

Sugimoto, H.; Kimura, Takayuki; Inoue, Shohei

doi:10.1021/ja983960i

Cited by 83 publications

(43 citation statements)

References 7 publications

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“…[13][14][15] Of more especial interest to us is the application of such an approach to complexes of transition-metal cations, such as Fe II or Fe III , which are likely to exhibit a spin-crossover phenomenon. [16][17][18][19][20] The approach led to the so-called ligand-driven lightinduced spin change (LD-LISC) phenomenon, [21][22][23][24] in which the optical switching of the photoreactive ligand (namely, the cisQ trans photoisomerization of styrylpyridine) causes a change of electronic structure that, in turn, may induce a high-spinQlow- We report an in-depth theoretical study of 4-styrylpyridine in its singlet S 0 ground state.…”

Section: Introductionmentioning

confidence: 99%

Ab Initio Static and Molecular Dynamics Study of 4‐Styrylpyridine

Daku¹,

Linarès²,

Boillot³

2007

ChemPhysChem

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We report an in-depth theoretical study of 4-styrylpyridine in its singlet S(0) ground state. The geometries and the relative stabilities of the trans and cis isomers were investigated within density functional theory (DFT) as well as within Hartree-Fock (HF), second-order Møller-Plesset (MP2), and coupled cluster (CC) theories. The DFT calculations were performed using the B3LYP and PBE functionals, with basis sets of different qualities, and gave results that are very consistent with each other. The molecular structure is thus predicted to be planar at the energy minimum, which is associated with the trans conformation, and to become markedly twisted at the minimum of higher energy, which is associated with the cis conformation. The results of the calculations performed with the post-HF methods approach those obtained with the DFT methods, provided that the level of treatment of the electronic correlation is high enough and that sufficiently flexible basis sets are used. Calculations carried out within DFT also allowed the determination of the geometry and the energy of the molecule at the biradicaloid transition state associated with the thermal cis=trans isomerization and at the transition states associated with the enantiomerization of the cis isomer and with the rotations of the pyridinyl and phenyl groups in the trans and cis isomers. Car-Parrinello molecular dynamics simulations were also performed at 50, 150, and 300 K using the PBE functional. The studies allowed us to evidence the highly flexible nature of the molecule in both conformations. In particular, the trans isomer was found to exist mainly in a nonplanar form at finite temperatures, while the rotation of the pyridinyl ring in the cis isomer was incidentally observed to take place within approximately 1 ps during the simulation carried out at 150 K on this isomer.

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Section: Introductionmentioning

confidence: 99%

Ab Initio Static and Molecular Dynamics Study of 4‐Styrylpyridine

Daku¹,

Linarès²,

Boillot³

2007

ChemPhysChem

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“…They offer a wide synthetic choice for creating varied molecular architectures and are being used as building blocks for the construction of artificial systems and catalysts for a verity of substrates [1][2][3][4][5][6][7][8][9][10][11][12][13][14]. The metalloporphyrins/ tetraazaporphyrins and ruthenium(II) polypyridyls are versatile and robust chromophores possessing strong visible region absorption and reversible redox behavior.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, spectroscopic and electrochemical investigations of supramolecular nickel(II)tetraazaporphyrin complexes

Prasad

Kumar

2005

J. Porphyrins Phthalocyanines

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The (bpy) 2 Ru II and (phen) 2 Ru II moieties were linked to [Ni(OBTTAP)] 1, periphery through coordinate bonds in order to synthesize cationic di-and pentanuclear complexes 2-5 that were obtained as PF 6 -salts. They were characterized by IR, 1 H NMR, UV-vis, and mass spectral data. The electronic absorption, emission and redox data of these bichromophoric systems indicate the presence of a high degree of intercomponent electronic interaction. The position and relative intensities of the Soret and Q bands in these complexes is altered due to peripheral binding of the metal units. The compounds were non-emissive for the Q band excitation but, Soret excitation led to a strong S 2 emission, observed between 400-450 nm. In cyclic voltammetry, the compounds exhibited one Ru centered oxidation together with one or two OBTTAP centered oxidations. The Ru II /Ru III oxidations were observed at significantly lower potentials as compared to the corresponding simple maleonitrilebenzylthioether complexes and has been interpretted in terms of weaker dπ(S)−dπ(Ru) interactions.

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“…The copper(II) to copper(I) photoreduction process was first evidenced by following the disappearance of the characteristic visible absorption band of 1, which is centered at 828 nm and arises from a d d transition. As shown in Figure 2, when a deoxy genated blue methanolic solution of 1 (1.9 mm) is irradiated at 365 nm, the complete disappearance of the 828 nm absorption band is observed within approximately 30 min and a limpid colorless solution, consistent with the formation of a cuprous [Cu(tBuBz 3 …”

mentioning

confidence: 88%

“…This assumes that the photoprocess is the only factor responsible for the changing absorption. [15] Direct evidence for the clean formation of a cuprous [Cu(tBuBz 3 + cation appear. In particular, all of the proton resonances of the tBuBz 3 tren ligand of the cuprous cation can be clearly identified at 7.28 and 7.06 ppm for the phenyl rings, and at 3.56, 2.78, and 1.27 ppm for the benzylic CH 2 , CH 2 N, and tBu groups, respectively.…”

Section: Tren)]mentioning

confidence: 99%

“…[1,2] Inoue and co workers reported a rare example of a photoswitchable catalyst based on the use of a bulky photoisomerizable styryl pyridine ligand which, in its Z form, activates an aluminium porphyrin catalyst through efficient coordination to the metal center. [3] Photoinduced electron transfer to a metal cation might represent a valuable strategy to switch on the activity of metal based catalysts that are inactive in their high valent oxidized form, but active in their low valent reduced form. This oxidation state dependent activity is typically observed for the copper(I) catalyzed alkyne azide cycloaddition (CuAAC) click reaction, [4] a major reaction currently exploited in all fields of the chemical sciences.…”

mentioning

confidence: 99%

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