Shun-Ze Zhan,*,† Wei Chen,† Weigang Lu,‡ Ji Zheng,‡ Fei Ding,† Tong Feng,† and Dan Li*,‡
Abastract: Three Cu3Pz3-based isostructural complexes (Cu3L3)2(CuX)2 (labeled as 1-ClO4, 1-NO3, and 1-Br, where X = ClO4-, NO3-, and Br-, respectively) were prepared by solvothermal reactions of an angular bifunctional pyridyl-pyrazole ligand, 4-(pyridin-4′-ylthio)-3,5-dimethyl-1Hpyrazole (HL), with Cu(ClO4)2, Cu(NO3)2, and CuBr, respectively. Pyrazolate (Pz) groups are highly specific to form planar trinuclear Cu3Pz3 units. Two Cu3L3 units are further connected by two CuX units through Npy-Cu-NPy (Py= 4-pyridyl) bonds to form an octanuclear chairlike molecule (Cu3L3)2(CuX)2, which then self-assembles through intertrimeric cuprophilicity to construct chainlike supraaggregates featuring two luminophores, [Cu3Pz3]2 and CuPy2X.With different counteranions (ClO4-, NO3-, and Br-), the complexes give off various emissions from red to green upon UV irradiation. 1-ClO4 and 1-NO3 show only low-energy (LE) orange (λemmax = 585 nm) and red (λemmax = 640 nm) emissions, while 1-Br exhibits excitation-dependent (260-360 nm) emissions from yellow to green due to variation in the relative intensities of two resolvable emissions, high energy (HE, λemmax = 520 nm) and LE (λem max = 630 nm). The dual emissions are assigned to 3CC (LE states) based on excimeric [Cu3Pz3]2 units and 3XLCT/3MLCT (HE states) based on CuPy2X units. This work realizes a chemopalette effect through regulations of the counteranion and excitation energy in a dual-emissive system. It provides valuable insights into the nature of dual-emissive materials and the further investigation of the photophysical mechanism in such a system.
文章链接：
acs.inorgchem.8b02203.pdf
