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JOURNAL OF MOLECULAR STRUCTURE, vol.1078, pp.90-105, 2014 (SCI-Expanded)
Conformational preferences for isolated molecules of ferrocene, 1-bromoferrocene and 1,1'-dibromoferrocene were obtained by combined use of matrix-isolation infrared spectroscopy and quantum chemical calculations. Monomeric ferrocene and 1-dibromoferrocene were found to exist in a low temperature argon matrix (T = 15 K) exclusively in the eclipsed configuration, which corresponds to their most stable conformation in gas phase. On the other hand, for the neat compounds in crystalline phase, intermolecular interactions induce conformational disorder, leading to presence in the room temperature polymorphic forms of monomeric units with the staggered (or nearly staggered) conformation. 1,1'-Dibromoferrocene exists in both gas phase and low temperature argon matrix in two conformers of C-2 symmetry (C-2-I and C-2-II), with eclipsed cyclopentadienyl moieties and Br atoms opposed to H atoms. The populations of the two conformers trapped in the as-deposited matrix were found to correspond to those estimated from theory for the room temperature equilibrium gas phase. By increasing the temperature of the matrix (up to 35 K), the gas phase lower energy form (C-2-I) converted to the C-2-II form. Besides allowing the precise structural and spectroscopic characterization of the two forms, these studies also revealed that the C-2-II conformer (having a largest dipole moment) is stabilized in the matrix media, thus becoming more stable than the C-2-I form under these conditions. Very interestingly, the room temperature stable polymorph of the compound (T-fus = 325.4 +/- 0.1 K) is composed by 1,1'-dibromoferrocene units exhibiting the C-2v symmetry eclipsed conformation with opposed bromine atoms, which for the isolated molecule corresponds to the highest energy conformation along the ring torsional coordinate and is the transition state structure between the two symmetry equivalent C-2-II minima. Differential scanning calorimetry, polarized light thermomicroscopy and infrared measurements on 1,1'-dibromoferrocene allowed to identify a new polymorph of the compound, with T-fus = 320.2 +/- 0.1 K. On the whole, the results presented in this article represent illuminating examples of intermolecularly-induced conformational disorder in solid phase and of its relevance to polymorphism. (C) 2013 Elsevier B.V. All rights reserved.