A Truly Isolated TCNQ•- Dimer?
Source abstract
Abstract
Crystals of (15-crown-5)2KTCNQ adopt a solid-state architecture built up from isolated TCNQ•- dimer units surrounded by crown-encapsulated cation “barrels” with no evidence for direct counterion interaction. The structural and spectroscopic behavior of this material therefore provides a valuable model for the solid-state behavior of an isolated TCNQ•- dimer.
Source: openalex_inverted_index · Quality: baseline
Research context
OpenAlex topics: Organic and Molecular Conductors Research · Porphyrin and Phthalocyanine Chemistry · Magnetism in coordination complexes
SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.
Affiliations
Department of Chemistry, The University Highfield, Southampton, SO17 1BJ UK
References (15)
Show source-provided references
1. Endres H. · 1980 · 3
2. Grossel M. C. · Chem. Mater. · 1994 · 6 · 810.1021/cm00044a007 ↗
3. Bartley S. L. · Angew. Chem. Int. Ed. Engl. · 1991 · 30 · 45010.1002/anie.199104481 ↗
4. Ballester L. · J. Chem. Soc., Chem. Commun. · 1991 · 1396 · 1397
5. Morinaga M. · Bull. Chem. Soc. Jpn. · 1980 · 53 · 122710.1246/bcsj.53.1221 ↗
6. Grossel M. C. · J. Phys. Org. Chem. · 1992 · 5 · 53910.1002/poc.610050816 ↗
7. Grossel M. C. · J. Chem. Soc., Chem. Commun. · 1992 · 1510 · 1512
8. Hynes R. C. · J. Chem. Soc., Faraday Trans. · 1991 · 87 · 2233
9. Crystallization
10. Data which were collected on an Enraf-Nonius CAD-4F diffractometer using monochromated Cu Kα radiation (full details are given in the supporting information). The unit cell and orientatation matrix were determined using automatic search and centering routines. Data were corrected for Lorentz and polarization effects and an empirical absorption correction based on the χ-scan data of one reflection was applied. There was no substantial crystal decay. The structure was solved by direct methods (SHELXS-86; Sheldrick, G., SHELXS-86 User Guide, Göttingen, FRG, 1986) and difference Fourier techniques were used to find most of the remaining non-hydrogen atoms. At this stage one atom was missing from each crown-ether and to find these the crown-ether moieties were restrained to have equivalent oxygen−oxygen distances (in the −OCH2CH2O− fragment) with an allowed esd of 0.01 Å, equivalent oxygen−potassium distances with an allowed esd of 0.01 Å and equivalent oxygen−potassium−oxygen angles (between a potassium and two adjacent oxygens) with an allowed esd of 0.01° (the oxygens used above were the atoms closest to the potassium atom). Under these restraints (which are reasonable for a 15-crown-5 crown-ether sandwich13) the missing atoms were found with difference Fourier maps and the oxygens assigned to the atoms closest to the potassium atom with the correct geometry. K(15-crown-5)2TCNQ (4): C32H44N4O10K1,M= 683.819, triclinic space groupP1̄,a= 9.462(1),b= 13.650(1),c= 14.213(3)Å, α = 98.61(1)°, β = 80.48(1)°, γ = 80.48(1)°,U= 1790.01 Å3,Z= 2,Dcalc= 1.2687 g cm-3,F(000) = 726. Data were collected using a crystal of 0.14 × 0.38 × 0.53 mm. A total of 7306 unique reflections were measured. The refinement converged to give a finalR= 0.130,Rw= 0.121. Atomic coordinates, bond lengths and angles, and thermal parameters have been deposited at the Cambridge Crystallographic Data Centre.
11. Arte P. E. · Acta Crystallogr., Sect. B · 1979 · 35 · 121710.1107/S0567740879005951 ↗
12. Minute 0. · J. Chem. Phys. · 1961 · 34 · 68510.1063/1.1701012 ↗
13. Morton J. R. · J. Chem. Phys. · 1989 · 90 · 215310.1063/1.456009 ↗
14. Vlasova R. M. · Sov. Phys.Solid State · 1969 · 10 · 2362
15. Reis A. H. · J. Am. Chem. Soc. · 1979 · 101 · 275610.1021/ja00504a058 ↗