Although atomically precise polyhydrido copper nanoclusters are of prime interest for a variety of applications, they have so far remained scarce. Herein, this work describes the synthesis of a dithiophosphate-protected copper(I) hydride-rich nanocluster (NC), [Cu
30H
18{S
2P(O
nPr)
2}
12] ( 1
H ), fully characterized by various spectroscopic methods and single-crystal X-ray diffraction. The X-ray structure of 1
H reveals an unprecedented central Cu
12 hollow icosahedron. Six faces of this icosahedron are capped by Cu
3 triangles, the whole Cu
30 core being wrapped by twelve dithiophosphate ligands and the whole cluster has ideal
S6 symmetry. The locations of the 18 hydrides in 1
H were ascertained by a single-crystal neutron diffraction study. They are composed of three types: capping μ
3-H, interstitial μ
4-H (seesaw) and μ
5-H ligands (square pyramidal), in good agreement with the DFT simulations. The numbers of hydrides and ligand resonances in the
1H NMR spectrum of 1
H are in line with their coordination environment in the solid state, retaining the
S6 symmetry in solution. Furthermore, two new Se-protected polyhydrido copper nanoclusters, [Cu
30H
18{Se
2P(OR)
2}
12] ( 2
H : R=
iPr 3
H : R=
iBu) were synthesized from their sulfur relative 1
H via ligand displacement reaction and their X-ray structures feature the exceptional case where both the NC shape and size are fully conserved during the course of ligand exchange. DFT and TD-DFT calculations allow understanding the bonding and optical properties of clusters 1
H – 3
H . In addition, the reaction of 1
H with [Pd(PPh
3)
2Cl
2] in the presence of terminal alkynes led to the formation of new bimetallic Cu−Pd alloy clusters [PdCu
14H
2{S
2P(O
nPr)
2}
6(C≡CR)
6] ( 4 : R=Ph; 5 : R = C
6H
4F).
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