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Title: Redox Ladder of Ni 3 Complexes with Closed‐Shell, Mono‐, and Diradical Triphenylene Units: Molecular Models for Conductive 2D MOFs
Abstract

We report the isolation and characterization of a series of trinickel complexes with 2,3,6,7,10,11‐hexaoxytriphenylene (HOTP), [(Me3TPANi)3(HOTP)](BF4)n(Me3TPA=N,N,N‐tris[(6‐methyl‐2‐pyridyl)methyl]amine) (n=2, 3, 4 for complexes1,2,3). These complexes comprise a redox ladder whereby the HOTP core displays increasingly quinoidal character as its formal oxidation state changes from −4, to −3, and −2 in1,2, and3, respectively. No formal oxidation state changes occur on Ni, allowing the isolation of singlet diradical, monoradical, and closed‐shell configurations for HOTP in1,2, and3, respectively, with a concomitant decrease in the spin coupling strength upon oxidation. Because the three complexes can be considered models of the smallest building blocks of 2D conductive metal‐organic frameworks such as Ni9HOTP4, these results serve as possible inspiration for the construction of extended materials with targeted electric and magnetic properties.

 
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NSF-PAR ID:
10308304
Author(s) / Creator(s):
 ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Angewandte Chemie International Edition
Volume:
60
Issue:
44
ISSN:
1433-7851
Page Range / eLocation ID:
p. 23784-23789
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
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