Synthesis, crystal structure and luminescent behaviour of coordination complexes of copper with bi- and tridentate amines and phosphonic acids

摘要

The synthesis and crystal structure of four new copper(I) and copper(II) supramolecular amine, and amine phosphonate, complexes is reported. Reaction of copper(I) with 2-,9-dimethyl-1-10-phenanthro_line (dmp) produced a stable 4-coordinate Cu(I) species, [Cu(I)(dmp)_2]CI_McOH_5H_2O (2), i.e., the increased steric hindrance in the 'bite' area of dmp did not prevent interaction with the metal and pro_vided protection against oxidation which was not possible for the phen analogue [R.Clarke, K. Latham, C. Rix, M. Hobday, J. White, CrystEngCommun. 7(3) (2005), 28-36]. Subsequent addition of phenylphosphonic acid to (2) produced two structures from alternative synthetic routes. An__in situ' process yielded red block Cu(I) crystals, [Cu~(I)(dmp)_2] _ [C_6H_5PO_3H_2_¤C_6H_5PO_3H] (4), whilst recrystallisation of (2) prior to addition of the acid (__stepwise' process) produced a green, needle-like Cull) complex, [Cu~(II)(dmp)_(H_2O)_2_¤C_6H_5PO_2(OH)][C_6H_5PO_2(OH)](3). However, addition of excess dmp during the 'stepwise' process forced the equilibrium towards product (4) and resulted in an optimum yield (99%). The structure of (4) was similar to the phen analogue, [Cu~(II)Cl(phen)_2]_[C_6H_5PO_2(OH)_¤C_6H_5P0(OH)_2](1)[R. Clarke, K. Latham, C. Rix, M. Hobday, J. White, CrystEngCommun. 7(3) (2005), 28-361, but the presence of dmp exerted some influence on global packing, whilst (3) exists as a polymeric layered material. In contrast, reaction of copper(I) with di-2-pyridyl ketone (dpk), followed by phenylphosphonic acid produced purple/blue Cu(II) species, [Cu~(II)(dpk_H_2O)_2] Cl_2 _ 4H_2O (5), and [Cu~(II)(dpk _ H_2O)_2] _ [C_6H_5PO_2(OH)_2 C_6H_5P0(OH)_2] (6), respectively, i.e., in both cases oxidation of copper occurred. Solid-state luminescence was observed in (2) and (4). The latter showing a 5-fold enhancement in intensity.