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  4. X/Y platinum(II) complexes: some features of supramolecular assembly via halogen bonding
 
research article

X/Y platinum(II) complexes: some features of supramolecular assembly via halogen bonding

Gitlina, Anastasia Yu.  
•
Petrovskii, Stanislav
•
Luginin, Maksim
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October 6, 2023
Dalton Transactions

Four series of new luminescent cyclometalated complexes [Pt(C^N)(IPy)Y] (HC^N = 2-phenylpyridine (Hppy), 2-(1-benzofuran-3-yl)pyridine (Hbfpy), methyl-2-phenylquinoline-4-carboxylate (Hmpqc), 2-(1-benzothiophen-3-yl)pyridine (Hbtpy), IPy = 4-iodopyridine, and Y = Cl, Br, I) have been investigated as X/Y 'building blocks' for the construction of a supramolecular network utilizing the I atom in IPy as a halogen bond (XB) donor (the X atom). The σ-hole of the X atom was found to provide non-covalent X⋯Y, X⋯Pt and X⋯π (π system of the metalated chelate ring) interactions for the complexes in the crystal state. NBO analysis confirms donation of the platinum electron density to iodine upon the X⋯Pt interaction. The nature of the X counterpart in XB depends on the nature of the Y atom and the cyclometalating ligand of the Pt(II) complex. DFT calculations show that the HOMO of [Pt(C^N)(IPy)Y] in the S_0 state is delocalized over Pt, Y and a C-coordinating fragment of C^N, while the LUMO in most complexes is formed by the Py orbitals of IPy. However, the alpha-HOMO in the lowest triplet state of [Pt(C^N)(IPy)Y] contains no contribution of the IPy wavefunctions. All Pt(II) complexes exhibited triplet luminescence in solution and in the solid state (Phi up to 0.129), which is determined by the nature of the C^N ligand. The emission profile is independent of the nature of the ligand Y, while the quantum yield decreases from Cl to I. Accordingly, on the basis of DFT calculation, this emission is interpreted as a C^N intraligand charge transfer predominantly. The XB formation did not show an effect on the luminescence of the complexes in the solid phase, however grinding of crystals results in an increase of brightness.

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Type
research article
DOI
10.1039/d3dt02970k
Web of Science ID

WOS:001085331900001

Author(s)
Gitlina, Anastasia Yu.  
Petrovskii, Stanislav
Luginin, Maksim
Melnikov, Alexey
Rychagova, Elena
Ketkov, Sergey
Grachova, Elena
Date Issued

2023-10-06

Published in
Dalton Transactions
Volume

52

Issue

43

Start page

16005

End page

16017

Subjects

Physical Sciences

•

M-X

•

Phosphorescence

•

Photophysics

•

Geometry

•

Br

•

Cl

•

Pd

Editorial or Peer reviewed

REVIEWED

Written at

EPFL

FunderGrant Number

The authors greatly appreciate the financial support from the Russian Science Foundation, grant 21-13-00052 (synthesis and photophysical investigations) and grant 23-13-00139 (quantum-chemical calculations). The work was carried out using equipment of St P

21-13-00052

Russian Science Foundation

Available on Infoscience
February 16, 2024
Use this identifier to reference this record
https://infoscience.epfl.ch/handle/20.500.14299/203885
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