A mechanophysical phase transition provides a dramatic example of colour polymorphism: the tribochromism of a substituted tri(methylene)tetrahydrofuran-2-one

Chemistry Central Journal

Abdullah M Asiri⁶  Harry G Heller¹  David S Hughes⁵  Michael B Hursthouse³  John Kendrick²  Frank JJ Leusen²  Riccardo Montis⁴ 

[1] School of Chemistry, Cardiff University, Cardiff CF10 3AT, Wales, UK

[2] School of Life Sciences, University of Bradford, Richmond Road, Bradford BD7 1DP, UK

[3] Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 21588, Saudi Arabia

[4] Dipartimento di Scienze Chimiche e Geologiche, Università degli Studi di Cagliari, Cittadella Universitaria, Monserrato I-09042, CA, Italy

[5] Chemistry, Faculty of Natural and Life Sciences, University of Southampton, Southampton SO17 1BJ, UK

[6] Center of Excellence for Advanced Materials Research (CEAMR), King Abdulaziz University, Jeddah 21589, Saudi Arabia

关键词: Colour polymorphism;    Molecular and lattice energy calculations;    Crystal structure analysis;    Tribochromism;    Photochromism;   

Others  :  1213787
DOI  :  10.1186/s13065-014-0070-3

 received in 2014-07-28, accepted in 2014-10-30,  发布年份 2014

【 摘 要 】

Background

Derivatives of fulgides have been shown to have interesting photochromic properties. We have synthesised a number of such derivatives and have found, in some cases, that crystals can be made to change colour on crushing, a phenomenon we have termed “tribochromism”. We have studied a number of derivatives by X-ray crystallography, to see if the colour is linked to molecular structure or crystal packing, or both, and our structural results have been supported by calculation of molecular and lattice energies.

Results

A number of 5-dicyanomethylene-4-diphenylmethylene-3-disubstitutedmethylene-tetrahydrofuran-2-one compounds have been prepared and structurally characterised. The compounds are obtained as yellow or dark red crystals, or, in one case, both. In two cases where yellow crystals were obtained, we found that crushing the crystals gave a deep red powder. Structure determinations, including those of the one compound which gave both coloured forms, depending on crystallisation conditions, showed that the yellow crystals contained molecules in which the structure comprised a folded conformation at the diphenylmethylene site, whilst the red crystals contained molecules in a twisted conformation at this site. Lattice energy and molecular conformation energies were calculated for all molecules, and showed that the conformational energy of the molecule in structure IIIa (yellow) is marginally higher, and the conformation thus less stable, than that of the molecule in structure IIIb (red). However, the van der Waals energy for crystal structure IIIa, is slightly stronger than that of structure IIIb – which may be viewed as a hint of a metastable packing preference for IIIa, overcome by the contribution of a more stabilising Coulomb energy to the overall more favourable lattice energy of structure IIIb.

Conclusions

Our studies have shown that the crystal colour is correlated with one of two molecular conformations which are different in energy, but that the less stable conformation can be stabilised by its host crystal lattice.

【 授权许可】

   
2014 Asiri et al.; licensee springer.

【 图 表 】

Figure 1.

Figure 2.

Figure 3.

Figure 4.

【 参考文献 】

• [1]Fan M-G, Yu L, Wei Z: Fulgide Family Compounds: Synthesis, Photochromism and Applications in Photochromic and Thermochromic Compounds. Plenum Press, New York; 1999.
• [2]Arunasalam VC, Baxter I, Drake SR, Hursthouse MB, Malik KMA, Otway DJ: Synthesis and characterization of the first group 2 mixed β-diketonate alkoxide complexes - X-ray crystal-structures of [Ca4(tmhd)4(OEt)4(EtOH)4], [Ca4(tmhd)6(OCH2CH2NMe2)2], and [H2Ba4(tmhd)6(OCH2CH2OPri)4]. Inorg Chem 1995, 34:5295-5306.
• [3]Avante-garde Materials Simulation: GRACE (Generation, Ranking, and Characterization Engine). Deutschland GmbH, Merzhauser Str. 177, 79100 Freiburg, Germany.
• [4]Neumann MA, Perrin MA: Energy ranking of molecular crystals using density functional theory calculations and an empirical van der Waals correction. J Phys Chem B 2005, 109:15531-15541.
• [5]Kresse G, Hafner J: Ab initio molecular-dynamics for liquid-metals. Phys Rev B 1993, 47:558-561. b. Kresse G, Furthmuller J: Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set.Physical Review B 1996, 54:11169–11186.
• [6]Wang Y, Perdew JP: Spin scaling of the electron-gas correlation-energy in the high-density limit. Phys Rev B 1991, 43:8911-8916.
• [7]Neese F: The ORCA program system. Wiley Interdiscip Rev 2012, 2:73-78.
• [8]Schafer A, Horn H, Ahlrichs R: Fully optimized contracted Gaussian-basis sets for atoms Li to Kr. J Chem Phys 1992, 97:2571-2577. b. Weigend F, Ahlrichs R: Balanced basis sets of split valence, triple zeta valence and quadruple zeta valence quality for H to Rn: Design and assessment of accuracy.Physical Chemistry Chemical Physics 2005, 7:3297–3305.
• [9]Grimme S, Antony J, Ehrlich S, Krieg H: A consistent and accurate ab initio parametrization of density functional dispersion correction (DFT-D) for the 94 elements H-Pu. J Chem Phys 2010, 132:19.
• [10]Schwabe T, Grimme S: Double-hybrid density functionals with long-range dispersion corrections: higher accuracy and extended applicability. Phys Chem Chem Phys 2007, 9:3397-3406.
• [11]Grimme S, Neese F: Double-hybrid density functional theory for excited electronic states of molecules. J Chem Phys 2007, 127:18.
• [12]Goerigk L, Moellmann J, Grimme S: Computation of accurate excitation energies for large organic molecules with double-hybrid density functionals. Phys Chem Chem Phys 2009, 11:4611-4620.
• [13]Sinnecker S, Rajendran A, Klamt A, Diedenhofen M, Neese F: Calculation of solvent shifts on electronic g-tensors with the conductor-like screening model (COSMO) and its self-consistent generalization to real solvents (Direct COSMO-RS). J Phys Chem A 2006, 110:2235-2245.
• [14]Cooper TG, Hejczyk KE, Jones W, Day GM: Molecular polarization effects on the relative energies of the real and putative crystal structures of valine. J Chem Theory Comput 2008, 4:1795-1805.
• [15]Gelbrich, T, Hursthouse, MB: A versatile procedure for the identification, description and quantification of structural similarity in molecular crystals.Crystengcomm 2005, 7; 324–336.
• [16]Asiri AMA, Heller HG, Hursthouse MB, Karalulov A: Tribochromic compounds, exemplified by 3-dicyclopropylmethylene-5-dicyanomethylene-4-diphenylmethylenetetrahydrofuran-2-one.Chemical Communications 2000:799–800
• [17]Macrae CF, Bruno IJ, Chisholm JA, Edgington PR, McCabe P, Pidcock E, Rodriguez-Monge L, Taylor R, van de Streek J, Wood PA: Mercury CSD 2.0 - New features for the visualization and investigation of crystal structures. J. Appl. Cryst 2008, 41:466-470.
• [18]Csikos E, Ferenczy GG, Angyan JG, Bocskei Z, Simon K, Gonczi C, Hermecz I: Colour polymorphism of a bis(quinoxaline) compound.Eur J Organ Chem 1999:2119–2125
• [19]Imai Y, Kinuta T, Nagasaki K, Harada T, Sato T, Tajima N, Sasaki Y, Kuroda R, Matsubara Y: Conformational and color polymorphism of achiral 2-methyl-3-(2-naphthalenylthio)-1,4-naphthalenedione. Crystengcomm 2009, 11:1223-1226.
• [20]Braun DE, Gelbrich T, Jetti RKR, Kahlenberg V, Price SL, Griesser UJ: Colored polymorphs: thermochemical and structural features of N-picryl-p-toluidine polymorphs and solvates. Crystal Growth Design 2008, 8:1977-1989.
• [21]Cruz-Cabeza AJ, Bernstein J: Conformational polymorphism. Chem. Rev. 2014, 114:2170-91.
• [22]Chan HCS, Kendrick J, Leusen FJJ: Molecule VI, a benchmark crystal-structure-prediction sulfonimide: are its polymorphs predictable? Angew Chem Int Ed 2011, 50:2979-2981.
• [23]Kendrick J, Leusen FJJ, Neumann MA, van de Streek J: Progress in crystal structure prediction. Chem A Eur J 2011, 17:10736-10744.
• [24]Montis R, Hursthouse MB, Chan HCS, Kendrick J, Leusen FJJ: Experimental and theoretical investigations of the polymorphism of 5-chloroacetoxybenzoic acid (5-chloroaspirin). Crystengcomm 2012, 14:1672-1680.
• [25]Kendrick J, Stephenson GA, Neumann MA, Leusen FJJ: Crystal structure prediction of a flexible molecule of pharmaceutical interest with unusual polymorphic behavior. Crystal Growth Design 2013, 13:581-589.
• [26]Chan HCS, Kendrick J, Neumann MA, Leusen FJJ: Towards ab initio screening of co-crystal formation through lattice energy calculations and crystal structure prediction of nicotinamide, isonicotinamide, picolinamide and paracetamol multi-component crystals. Crystengcomm 2013, 15:3799-3807.
• [27]Kendrick J, Montis R, Hursthouse MB, Leusen FJJ: “In-silico seeding”: Isostructurality and pseudoisostructurality in a family of aspirin derivatives. Crystal Growth & Design 2013, 13:2906-2915.
• [28]Gavezzotti A: Calculation of lattice energies of organic crystals: the PIXEL integration method in comparison with more traditional methods. Zeitschrift Fur Krist. 2005, 220:499-510.
• [29]Asiri AM, Ng SW: (E, E)-2-3,4-bis(4-methylbenzylidene)-5-oxotetrahydrofuran-2-ylidene propanedinitrile. Acta Crystallogr Sect E Struct Rep Online 2009, 65:0761-U2055.
• [30]Liang YC, Dvornikov AS, Rentzepis PM: New near infrared-sensitive photochromic fluorescing molecules. J Mater Chem 2003, 13:286-290.
• [31]Heller HG, Hughes DS, Hursthouse MB, Koh KVS: A new class of photochromic compounds exemplified by E-5-dicyanomethylene-4-(dialkyl and dicycloalkyl)methylene 1-(2,5-methyl-3-furyl) and (2-methyl-5-phenyl-3-thienyl)ethylidene tetrahydrofuran-2-ones.Journal of the Chemical Society-Chemical Communications 1994:2713–2714