Clarifying the Electronic Structure of Anion-Templated Silver Nanoclusters by Optical Absorption Spectroscopy and Theoretical Calculation.

Electronic structures of anion-templated silver nanoclusters (Ag NCs) are not well understood compared to conventional, template-free Ag NCs. In this study, we synthesized three new anion-templated Ag NCs, namely [S@Ag17(S-4CBM)15(PPh3)5]0, [S@Ag18(S-4CBM)16(PPh3)8]0, and [Cl@Ag18(S-4CBM)16(PPh3)8][PPh4], where S-4CBM = 4-chlorobenzene methanethiolate, and single-crystal X-ray crystallography revealed that they have S@Ag6, S@Ag10, and Cl@Ag10 cores, respectively. Investigation of their electronic structures by optical spectroscopy and theoretical calculations elucidated the following unique features: (1) their electronic structures are different from those of template-free Ag NCs described by the superatomic concept; (2) optical absorption in the range of 550-400 nm for S2--templated Ag NCs is attributed to the charge transitions from S2--templated Ag-cage orbitals to the s-shaped orbital in the S2- moiety; (3) the Cl--templated Ag NCs can be viewed as [Cl@Ag18(S-4CBM)16(PPh3)8]0[PPh4]0 rather than the ion pair [Cl@Ag18(S-4CBM)16(PPh3)8]-[PPh4]+; and (4) singlet-coupled singly occupied orbitals are involved in the optical absorption of the Cl--templated Ag NC.

Anion-templated silver nanoclusters: precise synthesis and geometric structure.

Metal nanoclusters (NCs) are gaining much attention in nanoscale materials research because they exhibit size-specific physicochemical properties that are not observed in the corresponding bulk metals. Among them, silver (Ag) NCs can be precisely synthesized not only as pure Ag NCs but also as anion-templated Ag NCs. For anion-templated Ag NCs, we can expect the following capabilities: 1) size and shape control by regulating the central anion (anion template); 2) stabilization by adjusting the charge interaction between the central anion and surrounding Ag atoms; and 3) functionalization by selecting the type of central anion. In this review, we summarize the synthesis methods and influences of the central anion on the geometric structure of anion-templated Ag NCs, which include halide ions, chalcogenide ions, oxoanions, polyoxometalate, or hydride/deuteride as the central anion. This summary provides a reference for the current state of anion-templated Ag NCs, which may promote the development of anion-templated Ag NCs with novel geometric structures and physicochemical properties.