From Mono- to Tetranuclear: A Silsesquioxane-Anchored Cu(I) Chromophore Array with Additive Absorption and Preserved Excited-State Properties
Abstract
Multichromophoric assemblies provide a practical route to increase light absorption without fundamentally altering the electronic structure of the individual chromophores. Here we report a tetranuclear heteroleptic Cu(I) complex in which four [Cu(N∧N)-(P ∧ P)] units are covalently attached to a double-decker silsesquioxane (DDSQ) scaffold. A structurally related mononuclear [Cu(N ∧ N)-(P ∧ P)] + complex (with N ∧ N = pyridyl-triazole; P ∧ P = DPEPhos) was used as a reference. The absorption and emission profiles of the tetranuclear assembly closely match those of the monomer, indicating that the local Cu(I) chromophore properties are largely preserved upon attachment to the DDSQ scaffold. At the same time, the MLCT absorption intensity increases approximately 4-fold (ε ≈ 17.3 vs. 4.1 • 10 3 M -1 cm -1 at 340 nm), consistent with chromophore multiplication and additive light harvesting. Electrochemical studies indicate that the tetranuclear scaffold largely preserves the mononuclear Cu(I)/ligand redox motif, with no clear evidence for electrochemical communication between the Cu(I) chromophores. Overall, DDSQ emerges as a versatile platform for constructing Cu(I) chromophore arrays that boost absorption cross sections while retaining monomer-like excited-state signatures.
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BibTeX
@article{liu2026from,
title = {{From Mono- to Tetranuclear: A Silsesquioxane-Anchored Cu(I) Chromophore Array with Additive Absorption and Preserved Excited-State Properties}},
author = {Yujia Liu and Lars E Burmeister and Clémence Queffélec and Nobuhiro Takeda and Masafumi Unno and Yann Pellegrin and Michael Karnahl and Armelle Ouali},
journal = {ACS Omega},
year = {2026},
month = aug,
doi = {10.1021/acsomega.6c06295},
url = {https://nantes-universite.hal.science/hal-05849516v1},
note = {CC BY-NC-ND 4.0},
}
RIS
TY - JOUR
TI - From Mono- to Tetranuclear: A Silsesquioxane-Anchored Cu(I) Chromophore Array with Additive Absorption and Preserved Excited-State Properties
AU - Yujia Liu
AU - Lars E Burmeister
AU - Clémence Queffélec
AU - Nobuhiro Takeda
AU - Masafumi Unno
AU - Yann Pellegrin
AU - Michael Karnahl
AU - Armelle Ouali
PY - 2026
DA - 2026/08/10
JO - ACS Omega
DO - 10.1021/acsomega.6c06295
UR - https://nantes-universite.hal.science/hal-05849516v1
AB - Multichromophoric assemblies provide a practical route to increase light absorption without fundamentally altering the electronic structure of the individual chromophores. Here we report a tetranuclear heteroleptic Cu(I) complex in which four [Cu(N∧N)-(P ∧ P)] units are covalently attached to a double-decker silsesquioxane (DDSQ) scaffold. A structurally related mononuclear [Cu(N ∧ N)-(P ∧ P)] + complex (with N ∧ N = pyridyl-triazole; P ∧ P = DPEPhos) was used as a reference. The absorption and emission profiles of the tetranuclear assembly closely match those of the monomer, indicating that the local Cu(I) chromophore properties are largely preserved upon attachment to the DDSQ scaffold. At the same time, the MLCT absorption intensity increases approximately 4-fold (ε ≈ 17.3 vs. 4.1 • 10 3 M -1 cm -1 at 340 nm), consistent with chromophore multiplication and additive light harvesting. Electrochemical studies indicate that the tetranuclear scaffold largely preserves the mononuclear Cu(I)/ligand redox motif, with no clear evidence for electrochemical communication between the Cu(I) chromophores. Overall, DDSQ emerges as a versatile platform for constructing Cu(I) chromophore arrays that boost absorption cross sections while retaining monomer-like excited-state signatures.
SN - 2470-1343
ER -