2026-10-12T21:17:32Z
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2026-09-14T14:03:51Z
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Ligand-Modulated Synthesis
of High-Nuclearity Copper
Nanoclusters Enables Photocatalytic Functionalization of C–Cl
and C–F Bonds
Arunachalam Sagadevan (3748120)
Mohammad Bodiuzzaman (4527175)
Atanu Ghosh (1287675)
Aleksander Shkurenko (1410853)
Naveen M. Halappa (24887049)
Simil Thomas (1801639)
Kathiravan Murugesan (7295900)
Bashir E. Hasanov (14001684)
Mutalifu Abulikemu (2285365)
Mohamed Nejib Hedhili (2590510)
Mohamed Eddaoudi (1367694)
Husam N. Alshareef (1512391)
Omar F. Mohammed (1262202)
Osman M. Bakr (1262199)
Magnus Rueping (1489489)
Biophysics
Biochemistry
Physical Sciences not elsewhere classified
Medicine
Cell Biology
Environmental Sciences not elsewhere classified
Chemical Sciences not elsewhere classified
Sociology
Information Systems not elsewhere classified
Inorganic Chemistry
Computational Biology
unactivated aryl chlorides
synergistic properties render
strong aggregation tendencies
state redox properties
standing challenge due
shell containing well
rapid redox cycling
effective photoredox catalyst
diphenylphosphino )- 1
c – cl
broad absorption tail
3 +</ sup
nuclearity copper nanoclusters
transient chelating ligand
modulate ligand arrangement
2 ′- bis
cn )< sub
44 </ sub
3 </ sub
nuclearity cu ncs
tert </
nuclearity cu
)– ncs
cu ncs
visible region
ultrafast assembly
structure features
modulated synthesis
mild conditions
intrinsic lability
favorable excited
extends continuously
electronic structure
driven strategy
controlled synthesis
air stability
>- butylbenzenethiol
4 -<
The controlled synthesis of high-nuclearity copper nanoclusters
(Cu NCs) remains a long-standing challenge due to the intrinsic lability,
rapid redox cycling, and strong aggregation tendencies of Cu(I)–NCs.
We introduce a BINAP (2,2′-bis(diphenylphosphino)-1,1′-binaphthyl)-assisted,
thiolate-driven strategy that enables the ultrafast assembly of a
high-nuclearity Cu NCs [Cu<sub>63</sub>(TBBT)<sub>44</sub>(CH<sub>3</sub>COOCH<sub>3</sub>)<sub>2</sub>(CH<sub>3</sub>CN)<sub>4</sub>(CH<sub>3</sub>OH)H<sub>14</sub>]<sup>3+</sup> (<b>Cu</b><sub><b>63</b></sub>). Notably, BINAP functions as a transient chelating
ligand that stabilizes Cu(I), moderates reduction kinetics, and suppresses
uncontrolled thiolate polymerization. The resulting <b>Cu</b><sub><b>63</b></sub> structure features a 12-atom Cu core capped
by a Cu<sub>51</sub>(TBBT)<sub>44</sub> (TBBT: 4-<i>tert</i>-butylbenzenethiol) shell containing well-defined surface vacancy
defects that modulate ligand arrangement and electronic structure. <b>Cu</b><sub><b>63</b></sub> exhibits a broad absorption tail
that extends continuously into the visible region, air stability,
and favorable excited-state redox properties. These synergistic properties
render the high-nuclearity Cu-cluster an effective photoredox catalyst
for the activation of unactivated aryl chlorides and fluorides under
mild conditions.
2026-09-14T00:00:00Z
Dataset
Dataset
10.1021/jacs.6c05496.s002
https://figshare.com/articles/dataset/Ligand-Modulated_Synthesis_of_High-Nuclearity_Copper_Nanoclusters_Enables_Photocatalytic_Functionalization_of_C_Cl_and_C_F_Bonds/33742140
CC BY-NC 4.0