Modulation of Metallophilic and π–π Interactions in Platinum Cyclometalated Luminophores with Halogen Bonding

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Modulation of Metallophilic and π–π Interactions in Platinum Cyclometalated Luminophores with Halogen Bonding. / Sivchik, Vasily; Kochetov, Aleksandr; Eskelinen, Toni; Kisel, Kristina S.; Solomatina, Anastasia I.; Grachova, Elena V.; Tunik, Sergey P.; Hirva, Pipsa; Koshevoy, Igor O.

In: Chemistry - A European Journal, Vol. 27, No. 5, 2021, p. 1787-1794.

Research output: Contribution to journal › Article › peer-review

BibTeX

@article{fb8ec2c454fa46bca998a4fab607c437,

title = "Modulation of Metallophilic and π–π Interactions in Platinum Cyclometalated Luminophores with Halogen Bonding",

abstract = "Luminescent cyclometalated complexes [M(C^N^N)CN] (M=Pt, Pd; HC^N^N=pyridinyl- (M=Pt 1, Pd 5), benzyltriazolyl- (M=Pt 2), indazolyl- (M=Pt 3, Pd 6), pyrazolyl-phenylpyridine (M=Pt 4)) decorated with cyanide ligand, have been explored as nucleophilic building blocks for the construction of halogen-bonded (XB) adducts using IC6F5 as an XB donor. The negative electrostatic potential of the CN group afforded CN⋅⋅⋅I noncovalent interactions for platinum complexes 1–3; the energies of XB contacts are comparable to those of metallophilic bonding according to QTAIM analysis. Embedding the chromophore units into XB adducts 1–3⋅⋅⋅IC6F5 has little effect on the charge distribution, but strongly affects Pt⋅⋅⋅Pt bonding and π-stacking, which lead to excited states of MMLCT (metal–metal-to-ligand charge transfer) origin. The energies of these states and the photoemissive properties of the crystalline materials are primarily determined by the degree of aggregation of the luminophores via metal–metal interactions. The adduct formation depends on the nature of the metal and the structure of the metalated ligand, the variation of which can yield dynamic XB-supported systems, exemplified by thermally regulated transition 3↔3⋅⋅⋅IC6F5.",

keywords = "crystal engineering, halogen bonding, luminescence, noncovalent interactions, platinum complexes, BONDED COCRYSTALS, CRYSTAL-STRUCTURES, STATE, PHOTOPHYSICAL PROPERTIES, PT(II) COMPLEXES, LUMINESCENCE, CHARGE-TRANSFER, INTERMOLECULAR INTERACTIONS, AGGREGATION, TERPYRIDINE COMPLEXES",

author = "Vasily Sivchik and Aleksandr Kochetov and Toni Eskelinen and Kisel, {Kristina S.} and Solomatina, {Anastasia I.} and Grachova, {Elena V.} and Tunik, {Sergey P.} and Pipsa Hirva and Koshevoy, {Igor O.}",

note = "Funding Information: The authors appreciate the financial support from the Academy of Finland (grant 317903, I.O.K.) and the Russian Science Foundation (grant 16‐13‐10064, photophysical investigations, E.V.G.). The work is part of the Academy of Finland Flagship Programme, Photonics Research and Innovation (PREIN), decision 320166. The photophysical studies were carried out using the core facilities of St Petersburg State University Research Park (Centre for Optical and Laser Materials Research, and Centre for Chemical Analysis and Materials Research).",

year = "2021",

doi = "10.1002/chem.202003952",

language = "English",

volume = "27",

pages = "1787--1794",

journal = "Chemistry - A European Journal",

issn = "0947-6539",

publisher = "Wiley-Blackwell",

number = "5",

}

RIS

TY - JOUR

T1 - Modulation of Metallophilic and π–π Interactions in Platinum Cyclometalated Luminophores with Halogen Bonding

AU - Sivchik, Vasily

AU - Kochetov, Aleksandr

AU - Eskelinen, Toni

AU - Kisel, Kristina S.

AU - Solomatina, Anastasia I.

AU - Grachova, Elena V.

AU - Tunik, Sergey P.

AU - Hirva, Pipsa

AU - Koshevoy, Igor O.

N1 - Funding Information: The authors appreciate the financial support from the Academy of Finland (grant 317903, I.O.K.) and the Russian Science Foundation (grant 16‐13‐10064, photophysical investigations, E.V.G.). The work is part of the Academy of Finland Flagship Programme, Photonics Research and Innovation (PREIN), decision 320166. The photophysical studies were carried out using the core facilities of St Petersburg State University Research Park (Centre for Optical and Laser Materials Research, and Centre for Chemical Analysis and Materials Research).

PY - 2021

Y1 - 2021

N2 - Luminescent cyclometalated complexes [M(C^N^N)CN] (M=Pt, Pd; HC^N^N=pyridinyl- (M=Pt 1, Pd 5), benzyltriazolyl- (M=Pt 2), indazolyl- (M=Pt 3, Pd 6), pyrazolyl-phenylpyridine (M=Pt 4)) decorated with cyanide ligand, have been explored as nucleophilic building blocks for the construction of halogen-bonded (XB) adducts using IC6F5 as an XB donor. The negative electrostatic potential of the CN group afforded CN⋅⋅⋅I noncovalent interactions for platinum complexes 1–3; the energies of XB contacts are comparable to those of metallophilic bonding according to QTAIM analysis. Embedding the chromophore units into XB adducts 1–3⋅⋅⋅IC6F5 has little effect on the charge distribution, but strongly affects Pt⋅⋅⋅Pt bonding and π-stacking, which lead to excited states of MMLCT (metal–metal-to-ligand charge transfer) origin. The energies of these states and the photoemissive properties of the crystalline materials are primarily determined by the degree of aggregation of the luminophores via metal–metal interactions. The adduct formation depends on the nature of the metal and the structure of the metalated ligand, the variation of which can yield dynamic XB-supported systems, exemplified by thermally regulated transition 3↔3⋅⋅⋅IC6F5.

AB - Luminescent cyclometalated complexes [M(C^N^N)CN] (M=Pt, Pd; HC^N^N=pyridinyl- (M=Pt 1, Pd 5), benzyltriazolyl- (M=Pt 2), indazolyl- (M=Pt 3, Pd 6), pyrazolyl-phenylpyridine (M=Pt 4)) decorated with cyanide ligand, have been explored as nucleophilic building blocks for the construction of halogen-bonded (XB) adducts using IC6F5 as an XB donor. The negative electrostatic potential of the CN group afforded CN⋅⋅⋅I noncovalent interactions for platinum complexes 1–3; the energies of XB contacts are comparable to those of metallophilic bonding according to QTAIM analysis. Embedding the chromophore units into XB adducts 1–3⋅⋅⋅IC6F5 has little effect on the charge distribution, but strongly affects Pt⋅⋅⋅Pt bonding and π-stacking, which lead to excited states of MMLCT (metal–metal-to-ligand charge transfer) origin. The energies of these states and the photoemissive properties of the crystalline materials are primarily determined by the degree of aggregation of the luminophores via metal–metal interactions. The adduct formation depends on the nature of the metal and the structure of the metalated ligand, the variation of which can yield dynamic XB-supported systems, exemplified by thermally regulated transition 3↔3⋅⋅⋅IC6F5.

KW - crystal engineering

KW - halogen bonding

KW - luminescence

KW - noncovalent interactions

KW - platinum complexes

KW - BONDED COCRYSTALS

KW - CRYSTAL-STRUCTURES

KW - STATE

KW - PHOTOPHYSICAL PROPERTIES

KW - PT(II) COMPLEXES

KW - LUMINESCENCE

KW - CHARGE-TRANSFER

KW - INTERMOLECULAR INTERACTIONS

KW - AGGREGATION

KW - TERPYRIDINE COMPLEXES

UR - http://www.scopus.com/inward/record.url?scp=85097619369&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/5f0005d1-5594-373c-8e49-3b8e446767b9/

U2 - 10.1002/chem.202003952

DO - 10.1002/chem.202003952

M3 - Article

C2 - 32970903

AN - SCOPUS:85097619369

VL - 27

SP - 1787

EP - 1794

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

SN - 0947-6539

IS - 5

ER -

ID: 70734444