Dataset Information

K?{[Fe^II(Tp)(CN)₃]₄[Co^III(^pzTp)]₃[Co^II(^pzTp)]}: a neutral soluble model complex of photomagnetic Prussian blue analogues.

ABSTRACT: Straightforward access to a new cyanide-bridged {Fe₄Co₄} "molecular box" containing a potassium ion, namely K?{[Fe^II(Tp)(CN)₃]₄[Co^III(^pzTp)]₃[Co^II(^pzTp)]} (1) (with Tp and ^pzTp = tris- and tetrakis(pyrazolyl)borate, respectively), is provided, alongside its full characterisation. A detailed analysis of the molecular structure (X-ray diffraction, mass spectrometry, NMR spectroscopy) and electronic properties (EPR spectroscopy, SQUID magnetometry, UV/Vis spectroscopy, cyclic voltammetry) reveals that 1 shows slow magnetic relaxation and a remarkable photomagnetic effect at low temperature which is reminiscent of some FeCo Prussian Blue Analogues (PBAs), and is ascribed to a photo-induced electron transfer. However, in contrast with these inorganic polymers, the overall neutral compound 1 is soluble and remarkably stable in organic solvents such as CH₂Cl₂. Moreover, 1 shows interesting redox versatility, with electrochemical experiments revealing the possible access to six stable redox states.

SUBMITTER: Garnier D

PROVIDER: S-EPMC6014070 | biostudies-literature | 2016 Aug

REPOSITORIES: biostudies-literature

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K⊂{[FeII(Tp)(CN)3]4[CoIII(pzTp)]3[CoII(pzTp)]}: a neutral soluble model complex of photomagnetic Prussian blue analogues.

Garnier D D Jiménez J-R JR Li Y Y von Bardeleben J J Journaux Y Y Augenstein T T Moos E M B EMB Gamer M T MT Breher F F Lescouëzec R R

Chemical science 20160513 8

Straightforward access to a new cyanide-bridged {Fe4Co4} "molecular box" containing a potassium ion, namely K⊂{[FeII(Tp)(CN)3]4[CoIII(pzTp)]3[CoII(pzTp)]} (1) (with Tp and pzTp = tris- and tetrakis(pyrazolyl)borate, respectively), is provided, alongside its full characterisation. A detailed analysis of the molecular structure (X-ray diffraction, mass spectrometry, NMR s ...[more]

PMID: 30155130

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Project description:The salt [K(18-crown-6)]2[Ru(CN)2(CO)3] ([K(18-crown-6)]2[1]) was generated by the reaction of Ru(C2H4)(CO)4 with [K(18-crown-6)]CN. An initial thermal reaction gives [Ru(CN)(CO)4]-, which, upon ultraviolet (UV) irradiation, reacts with a second equiv of CN-. Protonation of [1]2- gave [HRu(CN)2(CO)3]- ([H1]-), which was isolated as a single isomer with mutually trans cyanide ligands. The complex cis,cis,cis-[Ru(pdt)(CN)2(CO)2]2- ([2]2-) was prepared by the UV-induced reaction of [1]2- with propanedithiol (pdtH2). The corresponding iron complex cis,cis,cis-[Fe(pdt)(CN)2(CO)2]2- ([3]2-) was prepared similarly. The pdt complexes [2]2- and [3]2- were treated with Fe(benzylideneacetone)(CO)3 to give, respectively, [RuFe (μ-pdt)(CN)2(CO)4]2- ([5]2-) and [Fe2(μ-pdt)(CN)2(CO)4]2- ([4]2-). The pathway from [3]2- to Fe2 complex [4]2- implicates intermetallic migration of CN-. In contrast, the formation of [5]2- leaves the Ru(CN)2(CO) center intact, as confirmed by X-ray crystallography. The structure of [5]2- features a "rotated" square-pyramidal Fe(CO)2(μ-CO) site. NMR measurements indicate that the octahedral Ru site is stereochemically rigid, whereas the Fe site dynamically undergoes turnstile rotation. 57Fe Mössbauer spectral parameters are very similar for rotated [5]2- and unrotated Fe2 complex [4]2-, indicating the insensitivity of that technique to both the geometry and the oxidation state of the Fe site. According to cyclic voltammetry, [5]2- oxidizes at E1/2 ∼ -0.8 V vs Fc+/0. Electron paramagnetic resonance (EPR) measurements show that 1e- oxidation of [5]2- gives an S = 1/2 rhombic species, consistent with the formulation Ru(II)Fe(I), related to the Hox state of the [FeFe] hydrogenases. Density functional theory (DFT) studies reproduce the structure, 1H NMR shifts, and infrared (IR) spectra observed for [5]2-. Related homometallic complexes with both cyanides on a single metal are predicted to not adopt rotated structures. These data suggest that [5]2- is best described as Ru(II)Fe(0). This conclusion raises the possibility that for some reduced states of the [FeFe]-hydrogenases, the [2Fe]H site may be better described as Fe(II)Fe(0) than Fe(I)Fe(I).

Project description:Studies on molecular co-crystal type materials are important in the design and preparation of easy-to-absorb drugs, non-centrosymmetric, and chiral crystals for optical performance, liquid crystals, or plastic phases. From a fundamental point of view, such studies also provide useful information on various supramolecular synthons and molecular ordering, including metric parameters, molecular matching, energetical hierarchy, and combinatorial potential, appealing to the rational design of functional materials through structure-properties-application schemes. Co-crystal salts involving anionic d-metallate coordination complexes are moderately explored (compared to the generality of co-crystals), and in this context, we present a new series of isomorphous co-crystalline salts (PPh4)3[M(CN)6](H3PG)2·2MeCN (M = Cr, 1; Fe, 2; Co 3; H3PG = phloroglucinol, 1,3,5-trihydroxobenzene). In this study, 1-3 were characterized experimentally using SC XRD, Hirshfeld analysis, ESI-MS spectrometry, vibrational IR and Raman, 57Fe Mössbauer, electronic absorption UV-Vis-NIR, and photoluminescence spectroscopies, and theoretically with density functional theory calculations. The two-dimensional square grid-like hydrogen-bond {[M(CN)6]3-;(H3PG)2}∞ network features original {[M(CN)6]3-;(H3PG)4} supramolecular cis-bis(chelate) motifs involving: (i) two double cyclic hydrogen bond synthons M(-CN⋅⋅⋅HO-)2Ar, {[M(CN)6]3-;H2PGH}, between cis-oriented cyanido ligands of [M(CN)6]3- and resorcinol-like face of H3PG, and (ii) two single hydrogen bonds M-CN⋅⋅⋅HO-Ar, {[M(CN)6]3-;HPGH2}, involving the remaining two cyanide ligands. The occurrence of the above tectonic motif is discussed with regard to the relevant data existing in the CCDC database, including the multisite H-bond binding of [M(CN)6]3- by organic species, mononuclear coordination complexes, and polynuclear complexes. The physicochemical and computational characterization discloses notable spectral modifications under the regime of an extended hydrogen bond network.

Dataset Information

K?{[Fe^II(Tp)(CN)₃]₄[Co^III(^pzTp)]₃[Co^II(^pzTp)]}: a neutral soluble model complex of photomagnetic Prussian blue analogues.

Publications

K⊂{[Fe<sup>II</sup>(Tp)(CN)<sub>3</sub>]<sub>4</sub>[Co<sup>III</sup>(<sup>pz</sup>Tp)]<sub>3</sub>[Co<sup>II</sup>(<sup>pz</sup>Tp)]}: a neutral soluble model complex of photomagnetic Prussian blue analogues.

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Dataset Information

K?{[FeII(Tp)(CN)3]4[CoIII(pzTp)]3[CoII(pzTp)]}: a neutral soluble model complex of photomagnetic Prussian blue analogues.

Publications

K⊂{[Fe<sup>II</sup>(Tp)(CN)<sub>3</sub>]<sub>4</sub>[Co<sup>III</sup>(<sup>pz</sup>Tp)]<sub>3</sub>[Co<sup>II</sup>(<sup>pz</sup>Tp)]}: a neutral soluble model complex of photomagnetic Prussian blue analogues.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

K?{[Fe^II(Tp)(CN)₃]₄[Co^III(^pzTp)]₃[Co^II(^pzTp)]}: a neutral soluble model complex of photomagnetic Prussian blue analogues.