From Coordination to π-Hole Chemistry of Transition Metals: Metalloporphyrins as a Case of Study.
Angew Chem Int Ed Engl
; 63(38): e202409963, 2024 Sep 16.
Article
em En
| MEDLINE
| ID: mdl-38934220
ABSTRACT
Herein we have evidenced the formation of favorable π-hole Brâ
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metal noncovalent interactions (NCIs) involving elements from groups 9, 11 and 12. More in detail, M (M=Co2+, Ni2+, Cu2+ and Zn2+) containing porphyrins have been synthesized and their supramolecular assemblies structurally characterized by means of single crystal X-ray diffraction and Hirshfeld surface analyses, revealing the formation of directional Brâ
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M contacts in addition to ancillary hydrogen bond and lone pair-π bonds. Computations at the PBE0-D3/def2-TZVP level of theory revealed the π-hole nature of the Brâ
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M interaction. In addition, the physical nature of these NCIs was studied using Quantum Chemistry methodologies, providing evidence of π-hole Spodium and Regium bonds in Zn2+ and Cu2+ porphyrins, in addition to unveiling the presence of a π-hole for group 9 (Co2+). On the other hand, group 10 (Ni2+) acted as both electron donor and acceptor moiety without showing an electropositive π-hole. Owing to the underexplored potential of π-hole interactions in transition metal chemistry, we believe the results reported herein will be useful in supramolecular chemistry, organometallics, and solid-state chemistry by i) putting under the spotlight the π-hole chemistry involving first row transition metals and ii) unlocking a new tool to direct the self-assembly of metalloporphyrins.
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MEDLINE
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Ano de publicação:
2024
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Article