Photochemistry of transition metal octacyanides and related compounds. Past, present and future

Samotus, Alina; Szklarzewicz, Janusz

doi:10.1016/0010-8545(93)85008-r

Cited by 41 publications

(18 citation statements)

References 82 publications

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“…Thus in the case of those ions the calculated and measured data can be compared. It is well known, that especially for high coordination numbers (7,8), the structure of the complex ion strongly depends on the surroundings, especially on the type of cation and the presence of hydrogen bonds [22]. Although [M(CN) 8 ] 4) anions are usually dodecahedral [23] for its salts numerous geometries were found both in solution and in the solid state.…”

Section: Octacyanomolybdate and Pentacyanooxomolybdatementioning

confidence: 99%

The Transition Products in Substitutional Photochemistry of [Mo(CN)8]4− – Theoretical Approach. X-ray Crystal Structure of (AsPh4)[W(bpy)(CN)6]

Stawski

Szklarzewicz

Lewiński

2006

Transition Met Chem

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Section: Octacyanomolybdate and Pentacyanooxomolybdatementioning

confidence: 99%

The Transition Products in Substitutional Photochemistry of [Mo(CN)8]4− – Theoretical Approach. X-ray Crystal Structure of (AsPh4)[W(bpy)(CN)6]

Stawski

Szklarzewicz

Lewiński

2006

Transition Met Chem

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“…The (2) and -144.1(2) J K -1 mol -1 for quin -and 2,3-dipic -, respectively], indicating associative activation during the last step of the reaction (see Table 2), in agreement with the results found for the pic -complexes of Re(V) [21] and W(IV) [18]. It is anticipated that the strongly bonded cyano group will not dissociate easily and that substantial bond formation between the quinolinate anion and the metal complex takes place before the dissociation of the cyanide group.…”

Section: Discussionmentioning

confidence: 98%

“…The protonation and substitution reactions of the [MO 2 (CN) 4 ] n-ions (where M = Mo(IV), W(IV), Re(V) or Tc(V)) are well known and have been studied extensively [1][2][3][4][5]. These investigations have shown that these complexes undergo stepwise protonations to form the corresponding oxo-hydroxo, [MO(OH)(CN) 4 ] (n -1)-, and oxo-aqua, [MO(H 2 O)(CN) 4 ] (n -2)-, complexes with dissociation constants for the latter species: pK a1 = 10.0, pK a2 [ 14 (Mo); pK a1 = 7.8, pK a2 = 14.5 (W); pK a1 = 1.4, pK a2 = 3.7 (Re) [6].…”

Section: Introductionmentioning

confidence: 99%

Kinetic study of reaction of [ReN(H2O)(CN)4]2− with quinoline-2-carboxylate and pyridine-2,3-dicarboxylate anions

Mtshali

Purcell

Visser

et al. 2008

Transition Met Chem

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The kinetics of the reaction between [ReN(H 2 O)(CN) 4 ] 2-with different j 2 N,O-donor ligands (quin -and 2,3-dipic -, respectively) have been studied in the pH 4-12 range in aqueous solution. Two consecutive reaction steps with the formation of the [ReN(g 1 -quin)(CN) 4 ] 3-and [ReN(l 2 -quin) (CN) 3 ] 2-complexes, respectively, were spectrophotometrically observed and kinetically investigated. The same reaction mechanism is proposed for these two ligands. The first fast reaction (for quin -) is attributed to the aqua substitution of [ReN(H 2 O)(CN) 4 ] 2-with forward and reverse rate constants of 1.96(5) 9 10 -1 M -1 s -1 and 5.6(3) 9 10 -2 s -1 , while a rate of 2.64(3) M -1 s -1 was observed for the reaction between the conjugate base [ReN(OH)(CN) 4 ] 3-and quin -at 40.2°C. Due to small absorbance changes, it was difficult to obtain any good quality data for the fast reactions for 2,3-dipic -. The second, slower reaction is attributed to cyano substitution with rate constants (k 3 K 1 ) of 4.17(4) 9 10 -3 for quin -and 4.68(7) 9 10 -3 M -1 s -1 for 2,3-dipic -, at 80.02°C, respectively. The acid dissociation constant for the aqua complex was spectrophotometrically determined as 11.58(3) and 11.54(2) and kinetically as 11.51(8) and 11.41(1), at 80.4°C, respectively. Negative DS 6 ¼ values of -83.5(2) and -144.1(2) J K -1 mol -1 as well as the DH 6 ¼ of 71.4(3) and 47.3(3) kJ mol -1 , for the slow quin -and 2,3-dipic -reactions, respectively, point to an ordered transition state where bond formation is responsible for the major driving force of the reaction. The DH 6 ¼ ¼ 39:6ð2Þ kJ mol À1 and DS 6 ¼ ¼ À142:8ð1Þ J K À1 mol À1 for the fast forward reaction of quin -is indicative of expected associative activation in the transition state.

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“…The richness of the photochemistry of K 4 [MoCN 8 ]•2H 2 O in solution has been known for a few decades [1,2]. Irradiation of aqueous solutions of [MoCN 8 ] 4− in its ligand field bands (350-400 nm) allows photosubstitution reactions, with the isolation of different species, [MoCN 7 (H 2 O)] 3− or [MoCN 7 (OH)] 4− [3], that depend on the pH of the solutions.…”

Section: Introductionmentioning

confidence: 99%

New Photomagnetic Ionic Salts Based on [MoIV(CN)8]4− and [WIV(CN)8]4− Anions

Guionneau

Lafon

et al. 2021

Magnetochemistry

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Three new ionic salts containing [M(CN)8]4− (M = MoIV and WIV) were prepared using large complex cations based on a non-conventional motif built with the tris(2-aminoethyl)amine (noted hereafter tren) ligand, [{M’(tren)}3(μ-tren)]6+ (M’ = CuII and ZnII). The crystal structures of the three compounds show that the atomic arrangement is formed by relatively isolated anionic and cationic entities. The three compounds were irradiated with a blue light at low temperature, and show a significant photomagnetic effect. The remarkable properties of these compounds are (i) the long-lived photomagnetic metastable states for the [Mo(CN)8]4−-based compounds well above 200 K and (ii) the rare efficient photomagnetic properties of the [W(CN)8]4−-based compound. These photomagnetic properties are compared with the singlet-triplet conversion recently reported for the K4[Mo(CN)8]·2H2O compound.

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Photochemistry of transition metal octacyanides and related compounds. Past, present and future

Cited by 41 publications

References 82 publications

The Transition Products in Substitutional Photochemistry of [Mo(CN)8]4− – Theoretical Approach. X-ray Crystal Structure of (AsPh4)[W(bpy)(CN)6]

The Transition Products in Substitutional Photochemistry of [Mo(CN)8]4− – Theoretical Approach. X-ray Crystal Structure of (AsPh4)[W(bpy)(CN)6]

Kinetic study of reaction of [ReN(H2O)(CN)4]2− with quinoline-2-carboxylate and pyridine-2,3-dicarboxylate anions

New Photomagnetic Ionic Salts Based on [MoIV(CN)8]4− and [WIV(CN)8]4− Anions

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