Issue 13, 2023

Excited state processes of dinuclear Pt(ii) complexes bridged by 8-hydroxyquinoline

Abstract

Dinuclear d8 Pt(II) complexes, where two mononuclear square planar Pt(II) units are bridged in an “A-frame” geometry, possess photophysical properties characterised by either metal-to-ligand-(MLCT) or metal–metal–ligand-to-ligand charge transfer (MMLCT) transitions determined by the distance between the two Pt(II) centres. When using 8-hydroxyquinoline (8HQH) as the bridging ligand to construct novel dinuclear complexes with general formula [C^NPt(μ-8HQ)]2, where C^N is either 2-phenylpyridine (1) or 7,8-benzoquinoline (2), triplet ligand-centered (3LC) photophysics results echoing that in a mononuclear model chromophore, [Pt(8HQ)2] (3). The lengthened Pt–Pt distances of 3.255 Å (1) and 3.243 Å (2) results in a lowest energy absorption centred around 480 nm assigned as having mixed LC/MLCT character by TD-DFT, mirroring the visible absorption spectrum of 3. Additionally, 1 and 2 exhibit 3LC photoluminescence with limited quantum yields (0.008) from broad transitions centred near 680 nm. Photoexcitation of 1–3 leads to an initially prepared excited state that relaxes within 15 ps to a 3LC excited state centred on the 8HQ bridge, which then persists for several microseconds. All the experimental results correspond well with DFT electronic structure calculations.

Graphical abstract: Excited state processes of dinuclear Pt(ii) complexes bridged by 8-hydroxyquinoline

Supplementary files

Article information

Article type
Paper
Submitted
03 פבר 2023
Accepted
01 מרץ 2023
First published
01 מרץ 2023

Dalton Trans., 2023,52, 4008-4016

Author version available

Excited state processes of dinuclear Pt(II) complexes bridged by 8-hydroxyquinoline

S. Kromer, S. Roy, J. E. Yarnell, C. M. Taliaferro and F. N. Castellano, Dalton Trans., 2023, 52, 4008 DOI: 10.1039/D3DT00348E

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