期刊
MOLECULES
卷 28, 期 7, 页码 -出版社
MDPI
DOI: 10.3390/molecules28073247
关键词
cluster; copper; gold; luminescence; mechanochromism; thermochromism
The reaction of [Au(tht)(2)](ClO4), [Cu(CH3CN)(4)](ClO4), 3,6-di-tert-butyl-1,8-diethynyl-9H-carbazole (H(3)decz), and bis(2-diphenylphosphinophenyl)ether (POP) in the presence of triethylamine (NEt3) yielded the cluster complex Au4Cu2(decz)(2)(POP)(2) as yellow crystals. The Au4Cu2 cluster exhibits a scissor-like structure sustained by two decz and two POP ligands and stabilized by Au-Cu and Au-Au interactions. The cluster shows bright yellow to orange photoluminescence and exceptional thermochromic phosphorescence characteristics.
Reaction of [Au(tht)(2)](ClO4) (tht = tetrahydrothiophene), [Cu(CH3CN)(4)](ClO4), 3,6-di-tert-butyl-1,8-diethynyl-9H-carbazole (H(3)decz), and bis(2-diphenylphosphinophenyl)ether (POP) in the presence of triethylamine (NEt3) gave the cluster complex Au4Cu2(decz)(2)(POP)(2) as yellow crystals. As revealed by X-ray crystallography, the Au4Cu2 cluster exhibits scissor-like structure sustained by two decz and two POP ligands and stabilized by Au-Cu and Au-Au interactions. The Au4Cu2 cluster shows bright yellow to orange photoluminescence upon irradiation at >300 nm, arising from (3)[p (decz)?5d (Au)] (LMCT)-L-3 (ligand-to-metal charge transfer) and (3)[p?p* (decz)] (IL)-I-3 (intraligand) triplet states as revealed by theoretical and computational studies. When it is mechanically ground, reversible phosphorescence conversion from yellow to red is observed owing to more compact molecular packing and thus stronger intermetallic interaction. Variable-temperature luminescence studies reveal that it displays distinct red-shifts of the emission whether the temperature is elevated or lowered from ambient temperature, suggestive of exceptional thermochromic phosphorescence characteristics.
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