Staggered Assembly of a Dimeric Au₁₃ Cluster: Impacts on Coupling of Geometric Isomerism

Abstract

The specific states of aggregation of metal atoms in sub nanometer‐sized gold clusters are related to the different quantum confinement volumes of electrons, leading to novel optical and electronic properties. These volumes can be tuned by changing the relative positions of the gold atoms to generate isomers. Studying the isomeric gold core and the electron coupling between the basic units is fundamentally important for nanoelectronic devices and luminescence; however, appropriate cases are lacking. Here, the structure of the first staggered di‐superatomic Au25‐S was solved using single‐crystal X‐ray diffraction. The optical properties of Au25‐S were studied by comparing with eclipsed Au25‐E. From Au25‐E to Au25‐S, changes in the electronic structures occurred, resulting in significantly different optical absorptions originating from the coupling between the two Au13 modules. Au25‐S shows a longer electron decay lifetime of 307.7 ps before populating the lowest triplet emissive state, compared to 1.29 ps for Au25‐E. The experimental and theoretical results show that variations in the geometric isomerism lead to distinct photophysical processes owing to isomerism‐dependent electronic coupling. This study offers new insights into the connection between the geometric isomerism of nanosized building blocks and the optical properties of their assemblies, opening new possibilities for constructing function‐specific nanomaterials.

N^N^C-Cyclometalated rhodium(iii) complexes with isomeric pyrimidine-based ligands: unveiling the impact of isomerism on structural motifs, luminescence and cytotoxicity

“…the ability of compounds with identical molecular formulae to exist in spatially different forms is one of the most fundamental ideas in chemistry. [1][2][3] Revealing the impact of isomerism on crystal structures, [4][5][6][7][8][9][10][11][12] and chemical properties, [13][14][15][16][17][18][19][20][21] as well as physical [22][23][24][25][26][27][28][29][30][31][32][33][34] and biological properties [35][36][37][38][39] is of particular importance for establishing structure-property relationships which pave the way toward the more predictable design of substances with desirable properties. Despite various kinds of constitutional and configurational isomerism of metal complexes being well known, 40 ligand isomerism, which belongs to constitutional isomerism, is documented in literature to a considerably lesser extent than other types of the isomerism of complexes.…”

Influence of the substituents of the thiol ligand on the optical properties of AuCu14

“…7,8 Fortunately, it can be achieved through definite structure, high-level theory calculations and ultrafast transient absorption (TA) spectroscopy. 9–11…”