| Title: |
Fully Delocalized Mixed‐Valent Cu1.5Cu1.5 Complex: Strong Cu‐Cu interaction and Fast Electron Self‐Exchange Rate Despite Large Structural Changes** |
| Authors: |
Liu, Yang; Resch, Stefan G.; Chen, Haowei; Dechert, Sebastian; Demeshko, Serhiy; Bill, Eckhard; Ye, Shengfa; Meyer, Franc; 1 Institute of Inorganic Chemistry University of Göttingen Tammannstrasse 4 37077 Göttingen Germany; 3 State Key Laboratory of Catalysis Dalian Institute of Chemical Physics Chinese Academy of Sciences Dalian 116023 P. R. China; 2 Department of Inorganic Spectroscopy Max Planck Institute for Chemical Energy Conversion Stiftstraße 34–36 45470 Mülheim an der Ruhr Germany |
| Contributors: |
Liu, Yang; Resch, Stefan G.; Chen, Haowei; Dechert, Sebastian; Demeshko, Serhiy; Bill, Eckhard; Ye, Shengfa; Meyer, Franc; 1 Institute of Inorganic Chemistry University of Göttingen Tammannstrasse 4 37077 Göttingen Germany; 3 State Key Laboratory of Catalysis Dalian Institute of Chemical Physics Chinese Academy of Sciences Dalian 116023 P. R. China; 2 Department of Inorganic Spectroscopy Max Planck Institute for Chemical Energy Conversion Stiftstraße 34–36 45470 Mülheim an der Ruhr Germany |
| Publication Year: |
2023 |
| Collection: |
Georg-August-Universität Göttingen: GoeScholar |
| Description: |
A flexible macrocyclic ligand with two tridentate {CNC} compartments can host two Cu ions in reversibly interconvertible states, CuICuI (1) and mixed‐valent Cu1.5Cu1.5 (2). They were characterized by XRD and multiple spectroscopic methods, including EPR, UV/Vis absorption and MCD, in combination with TD‐DFT and CASSCF calculations. 2 features a short Cu⋅⋅⋅Cu distance (≈2.5 Å; compared to ≈4.0 Å in 1) and a very high delocalization energy of 13 000 cm−1, comparable to the mixed‐valent state of the biological CuA site. Electron self‐exchange between 1 and 2 is rapid despite large structural reorganization, and is proposed to proceed via a sequential mechanism involving an active conformer of 1, viz. 1′; the latter has been characterized by XRD. Such electron transfer (ET) process is reminiscent of the conformationally gated ET proposed for biological systems. This redox couple is a unique pair of flexible dicopper complexes, achieving fast electron self‐exchange closely related to the function of the CuA site. ; Dicopper complexes in the CuICuI and mixed‐valent Cu1.5Cu1.5 states have been synthesized and comprehensively characterized, revealing a high delocalization energy of the mixed‐valent species comparable with the biological CuA site. Fast electron self‐exchange is suggested to occur via a sequential ET pathway, involving an active conformational isomer of the flexible CuICuI species, pointing to a potential gating scenario for ET. image ; Alexander von Humboldt-Stiftung http://dx.doi.org/10.13039/100005156 ; Niedersächsische Ministerium für Wissenschaft und Kultur http://dx.doi.org/10.13039/501100010570 ; National Natural Science Foundation of China http://dx.doi.org/10.13039/501100001809 ; Deutsche Forschungsgemeinschaft http://dx.doi.org/10.13039/501100001659 |
| Document Type: |
article in journal/newspaper |
| Language: |
English |
| DOI: |
10.1002/anie.202215840 |
| Availability: |
https://resolver.sub.uni-goettingen.de/purl?gro-2/119335; https://resolver.sub.uni-goettingen.de/purl?gro-2/125003; https://doi.org/10.1002/anie.202215840 |
| Rights: |
info:eu-repo/semantics/openAccess ; CC BY-NC 4.0 ; http://onlinelibrary.wiley.com/termsAndConditions#vor |
| Accession Number: |
edsbas.4DBBA9AA |
| Database: |
BASE |