The crystal structures of three isomorphous trimesic acid channel inclusion complexes of polyhalide ions. A second example of triple catenation in the solid state

Herbstein, F. H.; Kapon, Moshe; Reisner, G. M.

doi:10.1098/rspa.1981.0093

Cited by 28 publications

(7 citation statements)

References 6 publications

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“…For I 3 - , X-ray crystallography − has shown that the ion is generally within 6° of linear but that the two I−I bond lengths may may differ by more than 6%. For I 5 - , geometries ranging from linear, , to a highly bent C 2 v structure, to an I 3 - ·I 2 complex have been observed. I 7 - and I 9 - seem to be less variable in the crystalline , state, exhibiting structures that can be described as I 2 ·I 3 - ·I 2 and I 2 ·I 5 - ·I 2 , respectively.…”

Section: Introductionmentioning

confidence: 94%

Ab Initio Calculations of the Ground Electronic States of Polyiodide Anions

Sharp

Gellene

1997

J. Phys. Chem. A

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Equilibrium bond lengths, harmonic frequencies, electron affinities, and dissociation energies (as appropriate) were determined for I, I-,I2, I2 -, and I3 - by CCSD(T) and four DFT methods (BLYP, BPW91, B3LYP, and B3PW91) using a basis set consisting of a relativistic effective core potential and a triple-zeta plus 2df polarization functions (ECP-TZ(2df)) for the valence electrons. Comparison of the DFT results with the CCSD(T) results and available experimental information indicates that the B3PW91 approach does particularly well describing the bonding in these species. B3PW91/ECP-TZ(2df) calculations of I5 - in linear (D ∞ h ) and bent (C 2 v ) geometries indicate that the linear structure is a low-energy transition state lying only about 0.1−0.2 eV above the C 2 v global minimum-energy structure. Harmonic frequencies and infrared and Raman intensities are calculated for both structures and compared to available experimental information.

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Section: Introductionmentioning

confidence: 94%

Ab Initio Calculations of the Ground Electronic States of Polyiodide Anions

Sharp

Gellene

1997

J. Phys. Chem. A

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“…To the best of our knowledge, the original consideration of these species, especially the larger ones, like I 5 - and I 7 - in the solution stemmed from the AI complex forming chemistry, and in view of the above ISE results it became necessary to re-examine the presence of polyiodide ions in the solution. It should be pointed out that the polyiodide ions such as I 3 - and I 5 - are known to exist − in solid crystal structures. However, their existence in aqueous solutions has never been confirmed.…”

Section: Introductionmentioning

confidence: 99%

Polyiodine and Polyiodide Species in an Aqueous Solution of Iodine + KI: Theoretical and Experimental Studies

Calabrese

Khan

2000

J. Phys. Chem. A

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In the presence of KI, iodine crystals dissolve rapidly in an aqueous solution forming triiodide ions (I 3 -) and other neutral species. The experimental evidence does not support the formation of polyiodide ions such as I 5 -, I 7 -, etc. in the solution. However, there is a strong evidence suggesting the formation of polyiodine species, I 2x , where x ) 2, 3, etc., stabilized by H + ions in the solution. Ab initio results are presented for structures and energies of some of these species with an x value of up to 4. Each geometry optimization was done at the HF/LANL2DZ level followed by a single-point energy calculation at the MP2/LANL2DZ level. These calculations suggest that the isolated polyiodine species are not stable and, among the complexed species, the protonated clusters are most stable. IntroductionIt is a common observation that the solubility of iodine crystals in water is remarkably increased when KI is added to the solution. It is believed by many that the polyiodide ions such as I 3 -, I 5 -, I 7 -, etc., form in the aqueous solution 1-6 and take part in the formation of blue amylose iodine (AI) or more commonly known as starch-iodine complex. While a number of researchers considered the involvement of I 3 -ions with the complex, 1,2 others considered the involvement of I 5 -ions, 3-5 I 7 -ions, 6 or species without any I -ions. 6,7 Because of the lack of direct experimental results, the above controversy remained undiminished until very recently. Our recent experiment 8 with an iodide ion selective electrode (ISE) suggests that the iodide ions are not consumed in the AI complex forming reaction even when these ions are present in the solution. This finding suggests that the iodide ions are not required for the AI complex formation and, hence, one can ignore the possible involvement of I 3 -, I 5 -, and I 7 -species with the complex.To the best of our knowledge, the original consideration of these species, especially the larger ones, like I 5 -and I 7 -in the solution stemmed from the AI complex forming chemistry, and in view of the above ISE results it became necessary to reexamine the presence of polyiodide ions in the solution. It should be pointed out that the polyiodide ions such as I 3 -and I 5 -are known to exist 9-14 in solid crystal structures. However, their existence in aqueous solutions has never been confirmed. Even though the gas-phase theoretical studies predict significant stability for each of the I 3 -and I 5 -ions (relative to separated constituent molecules and ions), 15 it is not known whether they can survive frequent collisions with solvent molecules in the solution. In an aqueous solution, the following reactions can be considered for the formation of large polyiodide species,

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“…A stoichiometric formula TMA·0.05TMA·0.04C 6 H 4 (COOH) 2 was reported (it seems that the exact nature of the dicarboxylic acid was not determined, but 1,3-dicarboxylic acid seems the most probable) . Isostructural polyhalide inclusion compounds of stoichiometric formula TMA·0.7H 2 O·0.09HI 5 , TMA·0.7H 2 O·0.09HBr 5 , and TMA·0.7H 2 O·0.167HIBr 2 have also been prepared from aqueous solutions. , In them, the polyhalide anion is located in the channels, while water and proton seem included in the roughly spherical voids. The variation of the cell parameters between these isomorphs denotes the flexibility of the supramolecular network of γ-TMA, related to the guest molecules accommodated into the channels.…”

Section: Resultsmentioning

confidence: 99%

A Flexible Hydrogen Bonded Organic Framework That Reversibly Adsorbs Acetic Acid: γ Trimesic Acid

Sanchez‐Sala

Vallcorba

Domingo

et al. 2018

Crystal Growth & Design

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The elusive γ phase of trimesic acid (TMA, 1,3,5-benzenetricarboxylic acid) has been prepared by recrystallization of commercial α-TMA in acetic acid. This process yields a modified γ-TMA phase that contains guest acetic acid solvent molecules with an approximate stoichiometry of γ-TMA·1HAc. According to 1H NMR and crystal structure determination, guest molecules are located both in the channels and in relatively isolated cavities. Despite the constricted connection between channels and cavities, solvent guest molecules are easily removed, even at room temperature, yielding guest-free γ-TMA. This process is reversible, since pristine γ-TMA can reabsorb acetic acid vapor at room temperature, yielding again γ-TMA·1HAc. Conversely, γ-TMA only adsorbs negligible amounts of N2 at 77 K or CO2 at 273 K, denoting that the guest–adsorbent interaction is a key factor governing adsorption.

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The crystal structures of three isomorphous trimesic acid channel inclusion complexes of polyhalide ions. A second example of triple catenation in the solid state

Cited by 28 publications

References 6 publications

Ab Initio Calculations of the Ground Electronic States of Polyiodide Anions

Ab Initio Calculations of the Ground Electronic States of Polyiodide Anions

Polyiodine and Polyiodide Species in an Aqueous Solution of Iodine + KI: Theoretical and Experimental Studies

A Flexible Hydrogen Bonded Organic Framework That Reversibly Adsorbs Acetic Acid: γ Trimesic Acid

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