Sakai Hayato, Hiramatsu Sunao, Akiyama Aoi, Negishi Yuichi, Hasobe Taku
Department of Chemistry, Faculty of Science and Technology, Keio University, Yokohama, Kanagawa 223-8522, Japan.
Department of Applied Chemistry, Faculty of Science, Tokyo University of Science, 1-3 Kagurazaka, Shinjuku-ku, Tokyo 162-8601, Japan.
J Am Chem Soc. 2025 Apr 23;147(16):13483-13490. doi: 10.1021/jacs.5c00337. Epub 2025 Apr 14.
A series of tetracene (Tc)-alkanethiol-functionalized gold nanoclusters (Au: = 25, 38) dyads with varying alkyl chain lengths ( = 5, 11) (denoted as Tc-C-Au) were synthesized to investigate the excited-state dynamics through the triplet excited state of these gold nanoclusters. Transient absorption measurements revealed bidirectional intramolecular energy transfer processes, including the initial singlet-singlet energy transfer (S-SEnT) from Tc to Au, followed by the subsequent triplet-triplet energy transfer (T-TEnT) from Au to Tc in Tc-C-Au ( = 5, 11), with nearly similar rate constants regardless of the alkyl chain length (). In the case of Tc-C-Au, intramolecular S-SEnT from Tc to Au was similarly observed; however, T-TEnT from Au to Tc was not detected. The differences in excited-state dynamics between Tc-C-Au and Tc-C-Au can be attributed to variations in the triplet energies of Au. These results clearly demonstrate the triplet character of Au and Au.
合成了一系列具有不同烷基链长度（(n = 5, 11)）的并四苯（Tc）-烷硫醇功能化金纳米团簇（Au：(N = 25, 38)）二元体系（表示为Tc-C-Au），以通过这些金纳米团簇的三重激发态研究激发态动力学。瞬态吸收测量揭示了双向分子内能量转移过程，包括在Tc-C-Au（(n = 5, 11)）中从Tc到Au的初始单重态-单重态能量转移（S-SEnT），随后是从Au到Tc的三重态-三重态能量转移（T-TEnT），无论烷基链长度（(n)）如何，速率常数几乎相似。在Tc-C-Au的情况下，同样观察到从Tc到Au的分子内S-SEnT；然而，未检测到从Au到Tc的T-TEnT。Tc-C-Au和Tc-C-Au之间激发态动力学的差异可归因于Au的三重态能量的变化。这些结果清楚地证明了Au和Au的三重态特性。
