| Inorganic-organic hybrid metal halide materials have been of great interest recently due to the useful properties offered by such a combination. The inorganic portions usually consisting of MX62- subunits, (M = Pb, Sn, Cd, Cu; X = Cl, Br, I) most often form 2-D perovskite layers where the metals are bridged by corner sharing halides. The organic portion, usually consisting of primary amines or anilines provides a template for the inorganic framework and in some cases, dictates the dimensionality (2-D, 1-D, 0-D) of the network. These materials have various applications in host-guest chemistry catalysis, and gas storage, or as superconductors or quantum dots.;It has been established by the Beatty group that it is possible to alter the metal halide assembly by changing the size of the substituent ortho to an aniline/amine group. Cadmium chloride complexes can be transformed from 2-D to 0-D based on the size of the substituent ortho to the nitrogen on a dianilinium complex. When the substituent in the ortho position is small (H) a perovskite layer is formed (Cd-Cl distance 2.4-2.7 A). If the substituent is changed to a methyl group the [CdCl6]2- layer expands (Cd-Cl distance 3.14-3.87 A). If the group is changed to a larger ethyl group, the steric bulkiness of the group causes the layer to collapse into a hexameric cluster with Cd-Cl distances that are slightly shorter than that of the expanded layer while still being longer than that of a normal perovskite layer (2.8-3.04 A). To determine if this phenomenon occurs generally, we have used metal halides such as CdX2 and CuX 2 (where X = Cl, Br, I) with a number of ortho-substituted anilines and dianilines (ortho = H, Cl, CH3, CH2CH3, CH(CH3)2, C(CH3)3, C6H 5). |
