Luminescent Complexes of the Trinuclear Silver(I) and Copper(I) Pyrazolates Supported with Bis(diphenylphosphino)methane

A A Titov; O A Filippov; A F Smol'yakov; I A Godovikov; J R Shakirova; S P Tunik; I S Podkorytov; E S Shubina

doi:10.1021/acs.inorgchem.9b00991

Luminescent Complexes of the Trinuclear Silver(I) and Copper(I) Pyrazolates Supported with Bis(diphenylphosphino)methane

Inorg Chem. 2019 Jul 1;58(13):8645-8656. doi: 10.1021/acs.inorgchem.9b00991. Epub 2019 Jun 19.

Authors

A A Titov¹, O A Filippov¹, A F Smol'yakov^{1

2

3}, I A Godovikov¹, J R Shakirova⁴, S P Tunik⁴, I S Podkorytov⁵, E S Shubina¹

Affiliations

¹ A. N. Nesmeyanov Institute of Organoelement Compounds , Russian Academy of Sciences , Vavilov Str., 28 , 119991 Moscow , Russia.
² Inorganic Chemistry Department , Peoples' Friendship University of Russia , Miklukho-Maklaya str. 6 , 117198 , Moscow , Russia.
³ Plekhanov Russian University of Economics , Stremyanny per. 36 , Moscow , 117997 , Russian Federation.
⁴ Institute of Chemistry , St. Petersburg State University Universitetskii pr., 26 198504 , St. Petersburg , Russia.
⁵ St. Petersburg State University , Laboratory of Biomolecular NMR , St. Petersburg , Universitetskaya nab. 7/9 , 199034 , Russia.

PMID: 31247857
DOI: 10.1021/acs.inorgchem.9b00991

Abstract

The first example of trinuclear copper(I) and silver(I) pyrazolates adducts with a tertiary diphosphine (Ph₂PCH₂PPh₂) retaining trimeric [MPz]₃ core is reported. Despite rather strong M-P bonding, the complexes are able to undergo the dissociation of one M-P bond leading to the "merry-go-round" movement of P atoms over the M₃ triangle. The copper complex displays emission from ¹MLCT and ³MLCT states. The triplet and singlet states are separated by a relatively small energy gap (1080 cm^-1) that triggers the thermally activated delayed fluorescence (TADF) behavior and leads to the worthy quantum yield of 41% at 298 K. The silver complex in the solid state and frozen solution shows dual emission originating from the ¹IL and ³MLCT states that is dictated by the much higher energy difference between the emissive singlet and triplet as well as by the essentially different nature of these states.