Reaction of potassium 3(5)-(2,5-dimethoxyphenyl)pyrazolate with 2-bromopyridine in diglyme (2,5,8-trioxanonane) at 130 °C for 3 d afforded 3-(2,5-dimethoxyphenyl)-1-(2-pyridyl)pyrazole (L¹) in 69% yield after an aqueous quench and recrystallisation from hexanes. Complexation of hydrated Cu(BF₄)₂ with 1 molar equivalent of L¹ and K[L^R] in CH₂Cl₂ afforded [CuL¹(L^R)]BF₄ [L^R = tris(3-arylpyrazolyl)hydroborate: R = Ph 1, 2-furyl 2, 2-thienyl 3, 4-tolyl 4, 4-FC₆H₄5 or 4-MeOC₆H₄6]. The single-crystal structures of 1·0.5H₂O and 2·2CH₂Cl₂ contain square-pyramidal complex cations with CuN₅ donor sets. Both structures show the presence of intramolecular graphitic interactions between the pendant dimethoxyphenyl group of L¹ and a R substituent from the L^R ligand. Treatment of Cu(BF₄)₂·xH₂O with 2 molar equivalents of L¹ in MeCN afforded [CuL¹₂][BF₄]₂7, the single-crystal structure of which shows a tetrahedrally distorted planar geometry about the Cu²⁺ ion with additional 2.9 Å Cu · · · O contacts to the 2-methoxy groups of each ligand, which ¹H NMR data suggest are retained in CD₃CN solution. Complexes 1–7 contain a {d_x²–y²}¹ copper(II) centre according to solution UV/VIS and EPR spectroscopies, 1–6 remaining five-co-ordinate in CH₂Cl₂ solution. Voltammetric measurements in CH₂Cl₂–0.5 mol dm^–3 NBuⁿ₄PF₆ at 293 K showed that E_½ for the L¹–[L¹]˙⁺ oxidation associated with the dimethoxyphenyl group of L¹ is unperturbed by the graphitic interaction involving this group in 1–6. However, for 1, 4 and 5 this couple is chemically reversible at scan rates between 10 and 1000 mV s^–1; for 2, 3 and 6 this process is partially obscured by an irreversible L^R ligand oxidation. For L¹ and 7, this process is quasi-reversible or irreversible under the same conditions. Hence, the intramolecular graphitic interactions in complexes 1, 4 and 5 may kinetically stabilise the dimethoxyphenyl radical cation against decomposition.