EXAFS Evidence That the CuCl64- Ion in (3-Chloroanilinium)8(CuCl6)Cl4 Has an Elongated Rather Than Compressed Tetragonal Geometry

Ellis, P.J.; Freeman, H.C.; Hitchman, Michael A.; Reinen, D.; Wagner, Burghard

doi:10.1021/ic00085a005

Cited by 40 publications

(31 citation statements)

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“…Unfortunately, two of the three σ 2 values reported by Ellis, Freeman and co-workers [51] are outside the chemically expected ranges at 0.008 and 0.0016 Å 2 for the 2.28 and 2.38 Å Cu\Cl bond-lengths, respectively (Fig. 6).…”

Section: [Cucl 6 ] 4− Revisitedmentioning

confidence: 76%

“…1 Fig. 6 shows the EXAFS analysis of a simple model complex containing [CuCl 6 ] 4− revisited [51]. It has long been known that the Jahn-Teller effect can, in theory, manifest through either axially elongated (Fig.…”

Section: Distortional Isomersmentioning

confidence: 99%

“…From arguments similar to those presented in Section 3.1.5 above, we calculate that both should have σ vib 2 values close to 0.0025 Å 2 . However, since the ab initio EXAFS code used by Ellis, Freeman and co-workers [51] was an early version of FEFF (version 4.06), we therefore decided to re-analyze their original data (taken from the supplementary material provided) using a newer version of the same code (version 9.5) in which the accuracy of the EXAFS amplitude calculations have been improved considerably. The results are summarized in Table 2 and provide gratifying confirmation of the seminal EXAFS study of Ellis, Freeman and co-workers [51], substantiating their conclusions with more chemically reasonable σ 2 values.…”

Section: [Cucl 6 ] 4− Revisitedmentioning

confidence: 99%

“…However, since the ab initio EXAFS code used by Ellis, Freeman and co-workers [51] was an early version of FEFF (version 4.06), we therefore decided to re-analyze their original data (taken from the supplementary material provided) using a newer version of the same code (version 9.5) in which the accuracy of the EXAFS amplitude calculations have been improved considerably. The results are summarized in Table 2 and provide gratifying confirmation of the seminal EXAFS study of Ellis, Freeman and co-workers [51], substantiating their conclusions with more chemically reasonable σ 2 values. In a subsequent and related study, EXAFS was used to show that the observation of six crystallographically equivalent Cu\N bonds of bis [tris(2-pyridyl)methane]copper(II) dinitrate is due to disorder of long and short Cu\N bonds about a three-fold axis and that the complex is actually a classic tetragonally elongated Jahn-Teller distorted species [55].…”

Section: [Cucl 6 ] 4− Revisitedmentioning

confidence: 99%

“…In order to illustrate the intellectual unrest that problems with a crystal structure can create we will briefly summarize the debate; the reader may find even the history of this confusing, but in Table 2 EXAFS curve-fitting analysis of the [CuCl 6 ] 4− in (3-chloroanilinium) 8 (CuCl 6 )Cl 4 revisited. The original data, taken from supplementary material [51], were fitted using modern theory and three alternative models. a Model 1 D 4h point-group, with axial elongation and equatorial compression, 2 D 4h point-group, with axial compression and equatorial expansion, and 3 D 2h point-group, distorted tetragonal structure.…”

Section: Co-crystallizationmentioning

confidence: 99%

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Section: [Cucl 6 ] 4− Revisitedmentioning

confidence: 76%

Section: Distortional Isomersmentioning

confidence: 99%

Section: [Cucl 6 ] 4− Revisitedmentioning

confidence: 99%

Section: [Cucl 6 ] 4− Revisitedmentioning

confidence: 99%

Section: Co-crystallizationmentioning

confidence: 99%

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Metalloprotein active site structure determination: Synergy between X-ray absorption spectroscopy and X-ray crystallography

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Copper Coordination Polymers with Infinite Chloride Ion Channels and Different Directions of the Jahn‐Teller Distortion, Built from Tris(1,2,4‐triazolyl)borate as a Modified Tris(pyrazolyl)borate Ligand

et al. 1996

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found Cul/CuZ-Cl = 2.572(2)/2.328(2), Cul/CuZ-N = 2.585(5)/2.077(4); 2.000(4)/1.979(5); 2.100(5)/2.734(5); 2.005(4)/1.994(4); 2.024(5)/2.369(5). In the 3-D coordination polymer 8 one of the two different Cu centers is chelated by the three endodentate nitrogen donors, while the other Cu center i s coordinated by three exodentate nitrogen atoms. The coordination sphere is completed in both cases by two hydroxo bridges to symmetry-related C u centers. The metalligand connectivity creates infinite channels with helical walls which contain the solvated chloride anions.The results presented here are part of an investigation of the rational assembly of coordination polymers and polynuclear metal complexes containing modifications of the popular poly@.vrazol-$)borate ligands (I) ['], such as hydrotris-and dihydrobis(l,2,4-triazolyflborate (2. 3)[2-41 or dihydrobis(telrazoly1)borale (4)[ips1. The additional donor atoms in 2-4 extend the molecular coordination "chemistry" of 1 to the dimension of the solid state by thc bridging action of the ligand and/or by the formation of hydrogen bonds with water of crystallization as an important elcment of the crystal architecture. Depending on the metal, the poly(triazoly1)borate ligands 2 and 3 were found to be able to function either as chelate ligands or as bridges between metal center~I~,~I. We demonstrate here that five or even all six nitrogen donor atoms o f the hydrotris-(trialzoly1)borate ligand 2 can cngage in metal coordination to give a polynuclear complex, schcinatically shown in 5, as part of a twoor three-dimensional framework, with additional interesting features. The crystal engineering of materials coinposed of inifinite two-and three-dimensional frameworks is an area of intense researchLh].When the labile homoleptic cobalt chelate complex 6[2a,31 is treated with CuClz in water a ligand exchange takes place to give cobalt-free copper compounds of 2 as products. The exact nature of the product depends on the reaction and work-up conditions as outlined in Scheme 1. A slow reaction at elevated temperature yields light blue needle-shaped crystals (7) with a borate ligand-tocopper-to-chlorine ratio of 1 : 1 : 1 directly from the reaction mixture. In contrast. a fast reaction gives a blue precipitate of yet unknown composition (but diffcrent from 7) which was recrystallized from Compounds 7 and 8 cxist as two-and three-dimcnsional coordination polymers, respectively, with two different copper enters each. according to single-crystal X-ray analyses. In 7 the CuC1N5 polyhedra of both copper ions arc approximately tctragonally elongated octahedra, as expccted due to vibronic Jahn-Teller coupling, and the polyhedra are formed by three endodentate and two exodentate nitrogen atoms from the triazolyl rings and a chlorine atom (Figure 1). Two of the triazolyl rings on each borate ligand bridge CuCl2[6l.

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The role of macrophage inhibitory factor in tumorigenesis and central nervous system tumors

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Cancer

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Poly(trimethoxy silylpropylaniline), a nanoporous (pore diameter of 2.4 nm), electroactive (stable reversible redox characteristics), electrochromic (yellow at −0.10 V, blue green at +0.50 V, and dark green at +0.70 V), and pH‐sensitive, silica–polyaniline (PANI) hybrid material (designated as KGM‐1) has been synthesized in powder form by a simple one‐pot chemical synthesis as well as a “thin nanolayered film” by cyclic voltammetry. High‐resolution transmission image of KGM‐1 informs that the particles are spherical, with diameters in the range of 0.5–1.5 μm. X‐ray diffraction pattern of pristine KGM‐1 confirms the combined presence of ordered silica network and PANI chains. The surface area of calcined KGM‐1 is 40 m2/g (∼15 times higher than KGM‐1), and the average pore size is 2.4 nm. The N2 adsorption features also inform that PANI is present as a uniform layer within the pores of silica and because of that the silica pores are not completely blocked. The reversible redox transitions in PANI units and nanoporosity of KGM‐1 are effectively used for the electro‐driven loading/release of DNA or adenosine 5′‐triphosphate. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010

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EXAFS Evidence That the CuCl64- Ion in (3-Chloroanilinium)8(CuCl6)Cl4 Has an Elongated Rather Than Compressed Tetragonal Geometry

Cited by 40 publications

References 1 publication

Metalloprotein active site structure determination: Synergy between X-ray absorption spectroscopy and X-ray crystallography

Metalloprotein active site structure determination: Synergy between X-ray absorption spectroscopy and X-ray crystallography

Copper Coordination Polymers with Infinite Chloride Ion Channels and Different Directions of the Jahn‐Teller Distortion, Built from Tris(1,2,4‐triazolyl)borate as a Modified Tris(pyrazolyl)borate Ligand

The role of macrophage inhibitory factor in tumorigenesis and central nervous system tumors

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