Regulation of π•••π stacking interactions between triimidazole luminophores and comprehensive emission quenching by coordination to Cu(II)

Eight Cu(ii) coordination compounds with cyclic triimidazole, triimidazo[1,2-a:1 ',2 '-c:1 '',2 ''-e][1,3,5]-triazine (L-1), its positional isomer, triimidazo[1,2-a:1 ',2 '-c:1 '',5 ''-e][1,3,5]-triazine (L-2), and two pyridine derivatives of L-1, 3-(pyridin-2-yl)triimidazo[1,2-a:1 ',2 '-c:1 '',2 ''-e][1,3,5]triazine (L-3) and 3-(pyridin-4-yl)triimidazo[1,2-a:1 ',2 '-c:1 '',2 ''-e][1,3,5]triazine (L-4) are reported. All compounds represent neutral Cu(ii) discrete complexes or coordination polymers comprising luminophore triimidazole molecules and charge-compensated anions. Starting from copper(ii) acetate monohydrate with the paddle-wheel geometry, two binuclear complexes [Cu-2(CH3COO)(4)(L-1)(2)] (1) and [Cu-2(CH3COO)(4)(L-3)(2)] (2), a mixed-dimensional 0D/1D coordination compound {[Cu-2(CH3COO)(4)(L-2)](2)[Cu-2(CH3COO)(4)(H2O)(L-2)]center dot 2(H2O)}(n) (3), all with binuclear paddle-wheel [Cu-2(CO2)(4)] secondary building units, and a mononuclear complex [Cu(CH3COO)(2)(L-2)(2)] (4) with square-planar N2O2 Cu(ii) coordination, were obtained. Starting from copper(ii) nitrate trihydrate, three mononuclear complexes [Cu(NO3)(2)(L-2)(4)]center dot 2CH(3)CN (5), [Cu(NO3)(2)(L-2)(4)]center dot 1.5(dmf) (6), and [Cu(NO3)(2)(H2O)(2)(L-4)(2)]center dot 2H(2)O (7) with Cu(ii) distorted octahedral N4O2 and N2O4 coordination cores, and 1D coordination polymer [Cu(NO3)(2)(L-3)](n) (8) with the distorted square pyramidal N2O3 Cu(ii) coordination geometry were obtained. In the mono- and binuclear complexes, luminophores L-1-L-4 coordinate as monodentate terminal ligands. In the coordination chain 3 the L-2 ligand acts as a bidentate-bridging exo-ligand, while in 8 the L-3 ligand acts as a bidentate-chelate one, and the structure extension to 1D is achieved via the bridging nitrate-anions. The compromise between the hydrogen bonds and pi center dot center dot center dot pi stacking interactions defines the stacking patterns of bulky luminophores coordinated to the metal center that vary from the dimeric associates to the infinite 2D motifs with the different overlapping areas of the stacking ligands. The strong aggregation-induced emission demonstrated by pure luminophores was nearly quenched in the reported Cu(ii) coordination compounds in the solid state.

Automated summary

Eight Cu(ii) coordination compounds with cyclic triimidazole ligands and its derivatives were reported. These compounds consist of neutral Cu(ii) discrete complexes or coordination polymers comprising luminophore triimidazole molecules and charge-compensated anions. The aggregation-induced emission demonstrated by pure luminophores was nearly quenched in the reported Cu(ii) coordination compounds in the solid state.