THz, Raman, IR and DFT studies of noncentrosymmetric metal dicyanamide frameworks comprising benzyltrimethylammonium cations.

We report density functional theory (DFT) studies of vibrational modes for benzyltrimethylammonium cations (BeTriMe) as well as THz, IR and Raman studies of [BeTriMe][M(dca)(HO)] (dca = N(CN), dicyanamide; M = Mn, Co, Ni) and their anhydrous analogues. These studies show that the anhydrous BeTriMeMn and BeTriMeNi have the same or very similar structures and loss of water molecules leads to significant changes in the metal-dicyanamide frameworks. In particular, the number of dca modes decreases, suggesting increase of crystal symmetry, probablly related with decrease in the number of non-equivalent dca bridges from two to one. Although it is possible that dehydration leads to a replacement of the coordinate Mn-O (Ni-O) bonds by Mn-N (Ni-N) bonds, wherein N atoms come from the C≡N groups of previously non-bridged dca units, reversibility of the dehydration process indicates that such new bonds are either not formed or are very weak. The anhydrous Mn and Ni compounds undergo similar reversible phase transitions to lower symmetry phases. The driving force for these transitions is most likely ordering of dca linkers but this process is accompanied by weak distortion of the metal-dicyanamide frameworks. In the case of BeTriMeCo, the loss of water molecules also leads to significant changes in the cobalt-dicyanamide framework. However, the structure of this analogue is different from the structures of the Mn and Ni counterparts, the number of unique dca linkers is preserved and the dehydration process is irreversible, suggesting more drastic rearrangement of the metal-dicynamide framework.