Synthesis and crystal structure of a heterometallic chromium-potassium one-dimensional chain

Li, Hui; Zhong, Zhuang Jin; You, Xiao‐Zeng; Chen, Wei

doi:10.1016/s0277-5387(96)00380-4

Cited by 5 publications

(6 citation statements)

References 12 publications

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“…, where TTF ¼ tetrathiafulvalene [40]. In this reported compound, the Cr is six-coordinate with tetradentate NAOP 2À in the equatorial plane and two NCS À in axial positions coordinated via N; the Cr-N and Cr-O (NAOP 2À ) distances were in agreement with those observed in other [27] Cr(III) Schiff-base complexes but the axial Cr-N bonds are slightly longer than those observed for [Cr(salen)(NCS) 2 K Á H 2 O] though both contain Cr(III). It appears that the nature and structure of the Schiff-base ligand have some influence on the axial Cr-N bond distances in these reported compounds.…”

Section: Electrochemical Resultssupporting

confidence: 88%

“…[Cr(OH 2 ) 2 (salophen)]NO 3 was prepared following a method described [27][28][29]. This compound (0.464 g, 1 mmol) was then dissolved in about 75 mL of methanol and reacted with four-fold excess of KSCN (0.389 g, 4 mmol) at RT for 24 h. The solution was filtered through a G-4 sintered glass crucible and the red-brown filtrate was left for slow evaporation at RT when dark red-brown compound separated.…”

Section: Synthesis Of K[cr(ncs) 2 (Salophen)] H 2 O (3)mentioning

confidence: 99%

“…The 2 ] were observed at 2078 s and 2102 m cm À1 , respectively [40]. On the other hand, only one strong (C¼N) band was observed [40] [27]. We have also synthesized the Cr(III) complex K[Cr(NCS) 2 (salophen)] Á H 2 O (3) following the reported methods [27][28][29] and recorded its spectra to get an insight about the difference in its electronic structure with that of 2.…”

Section: Electronic Spectramentioning

confidence: 99%

“…On the other hand, only one strong (C¼N) band was observed [40] [27]. We have also synthesized the Cr(III) complex K[Cr(NCS) 2 (salophen)] Á H 2 O (3) following the reported methods [27][28][29] and recorded its spectra to get an insight about the difference in its electronic structure with that of 2. Compound 3 also, like [Cr(salen)(NCS) 2 K Á H 2 O] displays only one strong (C¼N) band at 2079 cm À1 in its IR spectrum.…”

Section: Electronic Spectramentioning

confidence: 99%

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A paramagnetic octahedraltrans-dihydroxy chromium(IV) complex with dianionic tetradentate Schiff base salophen and crystal structure of itstrans-diisothiocyanato analog

Koley

Sivasubramanian

Varghese

et al. 2012

Journal of Coordination Chemistry

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A paramagnetic octahedral trans-dihydroxy chromium(IV) complex with dianionic tetradentate Schiff base salophen and crystal structure of its trans-diisothiocyanato analog, Journal of Coordination Chemistry, 65:20, 3623-3640, A paramagnetic octahedral trans-dihydroxychromium(IV) complex, [Cr(OH) 2 (salophen)] (1) (H 2 salophen ¼ N,N 0 -bis(salicylidene)-1,2-phenylenediamine), has been synthesized and characterized by elemental analysis, magnetic moment measurement, IR, UV-Vis, and EPR spectroscopic studies. Measured room temperature (RT) magnetic moment value is 2.79 BM for 1, indicating a d 2 (S ¼ 1) system with a triplet ground state. Compound 1 exhibits powder EPR spectra at RT and LNT, which show the allowed transition DM s ¼ AE1 (g ¼ 2.0038) as well as the ''forbidden'' half-field transition (DM s ¼ AE2) at g ¼ 4.2080. Two successive reduction waves are observed in the cyclic voltammogram of 1 in CH 3 CN at À0.84 and À1.63 V (vs. Ag/ AgCl), respectively. Compound 1 readily reacts with Mn 2þ ion, a Cr(IV)-specific reductant and also undergoes -OH substitution reactions in solution with NCS À and imidazole. The transdiisothiocyanato analog, [Cr(NCS) 2 (salophen)] (2), with eff ¼ 2.80 BM has been structurally characterized by X-ray crystallography and found to contain two N-bonded axial thiocyanato ligands with slightly different axial Cr-N bond lengths (N(3)-Cr(1), 2.032(2); N(4)-Cr(1), 2.015(2) Å ). Compound 2 and the corresponding Cr(III) compound K[Cr(NCS) 2 (salophen)] Á H 2 O (3) show significant difference in their electronic structures as revealed from their electronic spectra.

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Section: Electrochemical Resultssupporting

confidence: 88%

Section: Synthesis Of K[cr(ncs) 2 (Salophen)] H 2 O (3)mentioning

confidence: 99%

Section: Electronic Spectramentioning

confidence: 99%

Section: Electronic Spectramentioning

confidence: 99%

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A paramagnetic octahedraltrans-dihydroxy chromium(IV) complex with dianionic tetradentate Schiff base salophen and crystal structure of itstrans-diisothiocyanato analog

Koley

Sivasubramanian

Varghese

et al. 2012

Journal of Coordination Chemistry

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“…[39,40] The Cr-O Ph (1.93 Å) and Cr-N imine (2.01 Å) bond lengths in 5a are longer than the corresponding bonds in 4a and are in agreement with salen Cr III complexes with cyanide ligands. [41,42] During our studies on triplesalen ligand systems, we have shown that the free ligands are in the N-protonated tautomer with a heteroradialene resonance structure dominating. [25,[43][44][45] To investigate the extent of this heteroradialene contribution to the resonance hybrid, the bond lengths have been proven to be valuable tools.…”

Section: Structural Characterization Of Trinuclear Complexesmentioning

confidence: 91%

Trinuclear Triplesalophen Building Blocks with Terminal Cyanides and Implications for the Spin‐Polarization Mechanism for Low‐Spin Fe^III and Cr^III Ions

et al. 2018

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In order to further optimize our triplesalen-based single-molecule magnets, we have synthesized the triplesalophen ligand H 6 baron Me , where the completely sp 2 -hybridized ligand backbone should enable almost planar complexes. Here, we report the new complexes [(baron Me ){Fe III Cl} 3 ], [(baron Me )-{Fe III (CN) 2 } 3 ] 3-, and [(baron Me ){Cr III (CN) 2 } 3 ] 3-. As intended the local anisotropy axes, defined by the cyanide ligands, deviate only by ten degrees from the molecular C 3 -axis. The exchange coupling in [(baron Me ){Fe III (CN) 2 } 3 ] 3is ferromagnetic with J = 2.2 cm -1 but antiferromagnetic in [(baron Me ){Cr III (CN) 2 } 3 ] 3with J = -1.76 cm -1 . The ferromagnetic coupling in the Fe III low-spin complex is rationalized by a good π overlap of the d yz magnetic [a] 4987 orbital with the O(p z ) orbitals of the central phloroglucinol unit. The three unpaired electrons of the Cr III ions in [(baron Me )-{Cr III (CN) 2 } 3 ] 3provide competing spin-delocalization and spinpolarization pathways, which explains the overall antiferromagnetic coupling. These two complexes are the first l.s. Fe III and Cr III complexes of triplesalen-like ligands and emphasize the strong impact of the specific electronic configuration on the spin-polarization mechanism via the central phloroglucinol. The potential of [(baron Me ){Fe III (CN) 2 } 3 ] 3and [(baron Me ){Cr III -(CN) 2 } 3 ] 3as molecular building blocks for nonanuclear complexes by coordination to the six cyanides is discussed.have been prepared and characterized with many exhibiting interesting single-molecule magnet properties. [15][16][17][18][19][20][21][22][23][24] Scheme 1. Specific triplesalen and triplesalophen ligands. Scheme 2. Schematic presentation of the application of a [(baron Me ){M(CN) 2 } 3 ] 3building block for the supramolecular assembly of a) nonanuclear SMMs or b) triple-stranded 1D SCMs.the molecular building blocks enforcing a stronger collinearity of the local anisotropy tensors. In analogy to the successful synthesis of trinuclear SMMs by bridging two mononuclear salen complexes by a molecular building block with two trans coordinated cyano ligands, [4,5,27] our trinuclear triplesalophen complexes should be used as molecular building blocks for either nonanuclear SMMs (Scheme 2a) or triple-stranded one-dimensional single-chain magnets (Scheme 2b). We could already synthesize square-planar coordinated trinuclear Ni II 3 , Cu II 3 , and Co II 3 triplesalophen. [26,[28][29][30] Here, we report the first synthesis of the trinuclear molecular building blocks [(baron Me )-{Fe(CN) 2 } 3 ] 3and [(baron Me ){Cr(CN) 2 } 3 ] 3with six coordinated cyano ligands. These are also the first l.s. Fe III and Cr III complexes of extended phloroglucinol complexes that we have been unable to synthesize with any of our other ligands so far. That provides the opportunity to study the magnetic exchange mediated via the phloroglucinol for l.s. Fe III and Cr III ions for the first time. The coupling is ferromagnetic for l.s. Fe III and antiferromagneti...

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Synthesis, crystal structures and magnetic properties of charge transfer salts with anions containing Schiff base ligands

et al. 2006

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Synthesis and crystal structure of a heterometallic chromium-potassium one-dimensional chain

Cited by 5 publications

References 12 publications

A paramagnetic octahedraltrans-dihydroxy chromium(IV) complex with dianionic tetradentate Schiff base salophen and crystal structure of itstrans-diisothiocyanato analog

A paramagnetic octahedraltrans-dihydroxy chromium(IV) complex with dianionic tetradentate Schiff base salophen and crystal structure of itstrans-diisothiocyanato analog

Trinuclear Triplesalophen Building Blocks with Terminal Cyanides and Implications for the Spin‐Polarization Mechanism for Low‐Spin Fe^III and Cr^III Ions

Synthesis, crystal structures and magnetic properties of charge transfer salts with anions containing Schiff base ligands

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Synthesis and crystal structure of a heterometallic chromium-potassium one-dimensional chain

Cited by 5 publications

References 12 publications

A paramagnetic octahedraltrans-dihydroxy chromium(IV) complex with dianionic tetradentate Schiff base salophen and crystal structure of itstrans-diisothiocyanato analog

A paramagnetic octahedraltrans-dihydroxy chromium(IV) complex with dianionic tetradentate Schiff base salophen and crystal structure of itstrans-diisothiocyanato analog

Trinuclear Triplesalophen Building Blocks with Terminal Cyanides and Implications for the Spin‐Polarization Mechanism for Low‐Spin FeIII and CrIII Ions

Synthesis, crystal structures and magnetic properties of charge transfer salts with anions containing Schiff base ligands

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Trinuclear Triplesalophen Building Blocks with Terminal Cyanides and Implications for the Spin‐Polarization Mechanism for Low‐Spin Fe^III and Cr^III Ions