Noncovalent Axial I⋅⋅⋅Pt⋅⋅⋅I Interactions in Platinum(II) Complexes Strengthen in the Excited State

Standard

Noncovalent Axial I⋅⋅⋅Pt⋅⋅⋅I Interactions in Platinum(II) Complexes Strengthen in the Excited State. / Bulatov, Evgeny; Eskelinen, Toni; Ivanov, Alexander Yu; Tolstoy, Peter M.; Kalenius, Elina; Hirva, Pipsa; Haukka, Matti.

In: ChemPhysChem, Vol. 22, No. 20, 14.10.2021, p. 2044-2049.

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

Author

Bulatov, Evgeny ; Eskelinen, Toni ; Ivanov, Alexander Yu ; Tolstoy, Peter M. ; Kalenius, Elina ; Hirva, Pipsa ; Haukka, Matti. / Noncovalent Axial I⋅⋅⋅Pt⋅⋅⋅I Interactions in Platinum(II) Complexes Strengthen in the Excited State. In: ChemPhysChem. 2021 ; Vol. 22, No. 20. pp. 2044-2049.

BibTeX

@article{3c8201713039471e918a49c4349af653,

title = "Noncovalent Axial I⋅⋅⋅Pt⋅⋅⋅I Interactions in Platinum(II) Complexes Strengthen in the Excited State",

abstract = "Coordination compounds of platinum(II) participate in various noncovalent axial interactions involving metal center. Weakly bound axial ligands can be electrophilic or nucleophilic; however, interactions with nucleophiles are compromised by electron density clashing. Consequently, simultaneous axial interaction of platinum(II) with two nucleophilic ligands is almost unprecedented. Herein, we report structural and computational study of a platinum(II) complex possessing such intramolecular noncovalent I⋅⋅⋅Pt⋅⋅⋅I interactions. Structural analysis indicates that the two iodine atoms approach the platinum(II) center in a “side-on” fashion and act as nucleophilic ligands. According to computational studies, the interactions are dispersive, weak and anti-cooperative in the ground electronic state, but strengthen substantially and become partially covalent and cooperative in the lowest excited state. Strengthening of I⋅⋅⋅Pt⋅⋅⋅I contacts in the excited state is also predicted for the sole previously reported complex with analogous axial interactions.",

keywords = "axial interactions, excited state, iodine, noncovalent interactions, platinum, RECOGNITION, HYDROGEN-BOND, CRYSTAL-STRUCTURE, COORDINATION, OXIDATIVE ADDITION, NICKEL(II), METAL ATOMS, TRANSITION, LIGAND, INTERMOLECULAR INTERACTIONS",

author = "Evgeny Bulatov and Toni Eskelinen and Ivanov, {Alexander Yu} and Tolstoy, {Peter M.} and Elina Kalenius and Pipsa Hirva and Matti Haukka",

note = "Publisher Copyright: {\textcopyright} 2021 The Authors. ChemPhysChem published by Wiley-VCH GmbH.",

year = "2021",

month = oct,

day = "14",

doi = "10.1002/cphc.202100468",

language = "English",

volume = "22",

pages = "2044--2049",

journal = "Chemphyschem : a European journal of chemical physics and physical chemistry",

issn = "1439-4235",

publisher = "Wiley-Blackwell",

number = "20",

}

RIS

TY - JOUR

T1 - Noncovalent Axial I⋅⋅⋅Pt⋅⋅⋅I Interactions in Platinum(II) Complexes Strengthen in the Excited State

AU - Bulatov, Evgeny

AU - Eskelinen, Toni

AU - Ivanov, Alexander Yu

AU - Tolstoy, Peter M.

AU - Kalenius, Elina

AU - Hirva, Pipsa

AU - Haukka, Matti

PY - 2021/10/14

Y1 - 2021/10/14

N2 - Coordination compounds of platinum(II) participate in various noncovalent axial interactions involving metal center. Weakly bound axial ligands can be electrophilic or nucleophilic; however, interactions with nucleophiles are compromised by electron density clashing. Consequently, simultaneous axial interaction of platinum(II) with two nucleophilic ligands is almost unprecedented. Herein, we report structural and computational study of a platinum(II) complex possessing such intramolecular noncovalent I⋅⋅⋅Pt⋅⋅⋅I interactions. Structural analysis indicates that the two iodine atoms approach the platinum(II) center in a “side-on” fashion and act as nucleophilic ligands. According to computational studies, the interactions are dispersive, weak and anti-cooperative in the ground electronic state, but strengthen substantially and become partially covalent and cooperative in the lowest excited state. Strengthening of I⋅⋅⋅Pt⋅⋅⋅I contacts in the excited state is also predicted for the sole previously reported complex with analogous axial interactions.

AB - Coordination compounds of platinum(II) participate in various noncovalent axial interactions involving metal center. Weakly bound axial ligands can be electrophilic or nucleophilic; however, interactions with nucleophiles are compromised by electron density clashing. Consequently, simultaneous axial interaction of platinum(II) with two nucleophilic ligands is almost unprecedented. Herein, we report structural and computational study of a platinum(II) complex possessing such intramolecular noncovalent I⋅⋅⋅Pt⋅⋅⋅I interactions. Structural analysis indicates that the two iodine atoms approach the platinum(II) center in a “side-on” fashion and act as nucleophilic ligands. According to computational studies, the interactions are dispersive, weak and anti-cooperative in the ground electronic state, but strengthen substantially and become partially covalent and cooperative in the lowest excited state. Strengthening of I⋅⋅⋅Pt⋅⋅⋅I contacts in the excited state is also predicted for the sole previously reported complex with analogous axial interactions.

KW - axial interactions

KW - excited state

KW - iodine

KW - noncovalent interactions

KW - platinum

KW - RECOGNITION

KW - HYDROGEN-BOND

KW - CRYSTAL-STRUCTURE

KW - COORDINATION

KW - OXIDATIVE ADDITION

KW - NICKEL(II)

KW - METAL ATOMS

KW - TRANSITION

KW - LIGAND

KW - INTERMOLECULAR INTERACTIONS

UR - http://www.scopus.com/inward/record.url?scp=85112779158&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/aa969e4d-e177-39e4-9c93-16541893c28a/

U2 - 10.1002/cphc.202100468

DO - 10.1002/cphc.202100468

M3 - Article

C2 - 34328257

AN - SCOPUS:85112779158

VL - 22

SP - 2044

EP - 2049

JO - Chemphyschem : a European journal of chemical physics and physical chemistry

JF - Chemphyschem : a European journal of chemical physics and physical chemistry

SN - 1439-4235

IS - 20

ER -

ID: 85604613