**4. Experimental section**

Table 9 summarizes the applied methods of preparation of the monoacetylanthracenes and diacetylanthracenes. Melting points are uncorrected. All NMR spectra were recorded with Bruker DRX 500 MHz spectrometer. 1H-NMR spectra were recorded at 500.13 MHz using CDCl3 as solvent and as internal standard, δ(CDCl3)=7.263 ppm. 13C-NMR spectra were recorded at 125.75 MHz using CDCl3 as a solvent with internal standard, δ(CDCl3)=77.008 ppm. Complete assignments were made through 2-dimensional correlation spectroscopy (COSY, HSQC, HBMC and NOESY). Anthracene and nitrobenzene were obtained from Sigma-Aldrich; acetyl chloride and aluminum chloride were obtained from Acros. All the solvents were AR grade. Chloroform and dichloromethane were distilled before use. Single crystal X-ray diffraction was carried out on a Bruker SMART APEX CCD X-ray diffractometer, equipped with graphite monochromator and using MoKα radiation (λ=0.71073 Å). Low temperature was maintained with a Bruker KRYOFLEX nitrogen cryostat. The diffractometer was controlled by a Pentium-based PC running the SMART software package [Bruker AXS GmbH, 2002a]. Immediately after collection, the raw data frames were transferred to a second PC computer for integration and reduction by the SAINT program package [Bruker AXS GmbH, 2002b]. The structures were solved and refined by the SHELXTL software package [Bruker AXS GmbH, 2002c].

Polycyclic Aromatic Ketones – A Crystallographic and Theoretical Study of Acetyl Anthracenes 41

Agranat, I. & Shih, Y.-S. (1974) The Synthesis of Linearly Annelated Polycyclic Ketones by

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Table 9. Summary of methods of preparation of monoacetylanthracenes and diacetylanthracenes.

The quantum mechanical calculations were performed using the Gaussian03 [Frisch et al., 2004] package. Becke's three parameter hybrid density functional B3LYP [Becke, 1993], with the non-local correlation functional of Lee, Yang, and Parr [Lee et al., 1988] was used. The split valence 6-31G(d) basis set [Hariharan & Pople, 1973] was employed. All structures were fully optimized using symmetry constrains as indicated. Vibrational frequencies were computed at the same level of theory to verify the nature of the stationary points. For calculating the thermal corrections to Gibbs' free energy, the zero point energies were scaled by 0.9804 [Bauschlicher & Partridge, 1995].

#### **5. References**


Mala'bi et al.,2009

Bassilios, 1966

Bassilios, 1962

1997

Compound Method Solvent Melting Lit. Solvent Reference

1-AcAN Anthracene CH2Cl2 110 109 EtOH Bassilios, 1962

9-AcAN Anthracene CH2Cl2 78 75–76 MeCO2Et Bassilios, 1962

1,5-Ac2AN Anthracene CH2Cl2 215 213 CHCl3 Bassilios, 1963

1,8-Ac2AN Anthracene CH2Cl2 179 174–176 CHCl3 Sarobe & Jenneskens,

The quantum mechanical calculations were performed using the Gaussian03 [Frisch et al., 2004] package. Becke's three parameter hybrid density functional B3LYP [Becke, 1993], with the non-local correlation functional of Lee, Yang, and Parr [Lee et al., 1988] was used. The split valence 6-31G(d) basis set [Hariharan & Pople, 1973] was employed. All structures were fully optimized using symmetry constrains as indicated. Vibrational frequencies were computed at the same level of theory to verify the nature of the stationary points. For calculating the thermal corrections to Gibbs' free energy, the zero point energies were scaled

Adams, C. J., Earle, M. J., Roberts, G. & Seddon, K. R. (1998) Friedel–Crafts Reactions in

Agranat, I. & Shih, Y.-S. (1974) Haworth Synthesis as a Route to the Anthracene Ring

System. *Synthesis*, No. 12, pp. 865–867, ISSN: 0039-7881

Room Temperature Ionic Liquids. *Chemical Communications*, No. 19, pp. 2097–2098,

Et2O 247 249–250 CH2Cl2 Duerr, 1988

1,6-Ac2AN 2-AcAN ClC2H4Cl 170–172 171–172 MeCO2Et Gore, 1966

2-AcAN Anthracene C6H5NO2 177 174–178 MeCO2Et Mala'bi et al.,2009

 of point melting of preparation °C point, °C recryst.

2,7-Ac2AN 2-AcAN C6H5NO2 156–157 *i*PrOH

Table 9. Summary of methods of preparation of monoacetylanthracenes and

1,7-Ac2AN 2-AcAN ClC2H4Cl 102–103 – EtOH –

 AlCl3, Acetyl chloride

 AlCl3, Acetyl chloride

 AlCl3, Acetyl chloride

 AlCl3, Acetyl chloride

 AlCl3, Acetyl chloride

 AlCl3, Acetyl chloride

 AlCl3, Acetyl chloride

 AlCl3, Acetyl chloride

anthracene, MeLi

dicarbomethoxy-

by 0.9804 [Bauschlicher & Partridge, 1995].

ISSN: 1364-548X

9,10-Ac2AN 9,10-

diacetylanthracenes.

**5. References** 


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**2** 

*México* 

**Calix[8]arenes Solid-State Structures:** 

David J. Hernández and Ivan Castillo *Universidad Nacional Autónoma de México* 

**Derivatization and Crystallization Strategies** 

The macrocycles known as calix[*n*]arenes, where *n* represents the number of phenolic units bridged by methylene groups, represent ideal building blocks in supramolecular chemistry for the development of scaffolds with a preorganized structure, a well-defined cavity size, and modifiable positions for the introduction of a variety of functional groups, as shown in Fig. 1 (Böhmer, 1995; Asfari et al., 2001). The development of novel calixarene derivatives with the capability to act as receptors, sensors, catalysts, or ion transporters designed for specific purposes has been exploited to a great extent with the smaller member of the family calix[4]arene, and to a lesser degree with calix[6]arene. In the particular case of calix[4]arenes, the ease of modification by introduction of several types of functional groups at the phenolic rim has led to the development of numerous examples of versatile compounds (Baklouti et al., 2006; Baldini et al., 2007). The variety of derivatives reported to date is related to the well established synthetic protocols, which allow the preparation of calix[4]arenes with regio- and atropisomeric control by deprotonation of the phenolic OH groups with specific alkali-metal bases. These synthetic methods have been extended to the more recently developed thiacalix[4]arenes, which feature sulfur atoms as bridging groups

The development of systems based on the larger members of the calixarene and thiacalixarene families, namely calix[8]arene and thiacalix[8]arene (from now on referred to indiscriminately as calix[8]arenes), has been slow relative to its smaller analogues. This is likely due to the number of phenolic OH and aromatic positions available for functionalization, for which the regioselective introduction of substituents remains a challenging synthetic task. As a consequence, reports on crystallographically characterized calix[8]arene derivatives are relatively sparse. While the solution structures can be determined by a variety of methods, notably NMR spectroscopy, crystallographic characterization still represents the most reliable proof of the spatial arrangement of the macrocycles, particularly when the mobility of the large calix[8]arene is concerned. The limited availability of structural data is likely related to the large number of degrees of freedom present in the larger macrocycles, which does not allow the long-range ordering required for single-crystal formation. A search of the Cambridge Structural Database affords 89 structures of methylene-bridged calix[8]arenes, compared to the numbers of the four- and

**1. Introduction** 

between the phenolic components.

six-member macrocycles (Table 1).

