Highly photoluminescent poly(norbornene)s carrying platinum–acetylide complex moieties in their side chains: evaluation of oxygen sensing and TTA–UC

Abstract

Ring-opening metathesis polymerization (ROMP) of norbornene derivatives is useful for preparing thermally stable and transparent polymeric materials with good moldability. This study deals with ROMP of norbornene monomer 1 bearing...

End Functionalization of Polynorbornene with Platinum–Acetylide Complexes Utilizing a Cross-Metathesis Reaction

“…The UC quantum yield of poly(1b) with 9,10-diphenylanthracene was 41%, higher than those of the previously reported polynorbornenes bearing Pt−acetylide complex moieties at the side chains (25−32%), 43 as summarized in Table S6. In the previously reported side-chain-type polymers, the sensitizers (Pt−acetylide complex moieties) possibly locate in close proximity to each other, resulting in partial aggregation and reabsorption of UC emission at the side chains, leading to a decrease in UC quantum yields.…”

“…Rather than simply adding such complexes to polymers, it would be desirable to chemically bond Ptcomplexes to polymer chains to avoid bleeding out. We recently synthesized polynorbornenes bearing Pt−acetylide complex moieties at the side chains, 43 which feature O 2 sensing and TTA-UC, but no remarkable difference in photoluminescence properties was observed between the polymers and the corresponding monomers. It seems that the molecular environment of the Pt−acetylide complex moieties is not largely different from side-chain-functionalized polymers and the corresponding monomeric complexes.…”

“…The Supporting Information is available free of charge at https://pubs.acs.org/doi/10.1021/acs.macromol.2c01882. Experimental section; 1 H, 13 C, and 31 P NMR spectra of the monomers, precursors, model compounds, and poly­( 1b ) (Figures S1–S20); IR spectra of the monomers, model compounds, and poly­( 1b ) (Figures S21–S27); SEC traces of the monomers, model compounds, and polymers (Figures S28–S37); ESI-TOF MS charts of the monomer (Figures S38–S40); MALDI-TOF MS charts and representative peaks of poly­( 1 ) and poly­( 1 )′ (Figure S41 and Tables S1 and S2); yields and SEC data of polymers (Table S3); photoluminescence spectra of 4a , a mixture of poly­( 1 ) + 4a and poly­( 1a ) (Figure S42), photoluminescence spectra of poly­( 1b ), 4b , and a mixture of poly­( 1 ) and 4b (Figure S43); synthetic scheme of the polynorbornenes bearing Pt–acetylide moieties at the side chains previously reported (Scheme S8); photophysical properties of poly­( 1b ), 4b and a mixture of poly­( 1 ) and 4b (Tables S4 and S5); UC properties of poly­( 1b ) and polynorbornenes bearing Pt–acetylide moieties at the side chains (Table S6); UV–vis absorption spectra of PMMA films containing 4b and poly­( 1b ) (Figure S44); photoluminescence spectra of PMMA films containing poly­( 1b ) and 4b before normalization (Figure S45); IR absorption spectra of monomeric models of poly­( 1 )′ and poly­( 1a ) simulated by the DFT method (Figure S46); UV–vis absorption, fluorescence, and phosphorescence spectra of 4a and 4b simulated by the TD-DFT method (Figures S47–S51); fluorescence decay curves of poly­( 1b ), 4b and a mixture of poly­( 1 ) + 4b (Figure S52); CIE coordinates of poly­( 1b ) and 4b (Figure S53); TGA traces of 4b , poly­( 1b ) and a mixture of poly­( 1 ) + 4b (Figure S54); DSC traces of poly­( 1a ), poly­( 1b ), and poly­( 1 ) (Figure S55); and calculations for theoretical weight loss (PDF) Geometry data for compounds optimized by the DFT method, which are combined in a single text file readable by Mercury (XYZ) Movies of solutions and PMMA films containing poly­( 1b ) and 4b under irradiation of UV light with and without Ar bubbling/feeding (Movie 1) (MP4) Photograph of PMMA films containing poly­( 1b ) and 4b under irradiation of UV light with and without Ar feeding (Movie 2) (MP4) …”

Synthesis of platinum-containing oligomers utilizing ADMET chemistry and polycondensation of a bisimide with α,ω-dibromoalkanes: examination of triplet–triplet annihilation upconversion

“…Monomer 1 exhibited an IR absorption peak at 2083 cm −1 attributable to the stretching vibration of carbon-carbon triple bond attached to the Pt atom, in a manner like its analogues. 14,15,26 On the other hand, bisnaphthalimide monomer 2 bearing a Pt-acetylide complex moiety was synthesized according to Scheme S2, † also starting from 4-bromo-1,8-naphthalimide in three steps. Monomer 2 was poorly soluble in common organic solvents including CHCl 3 , CH 2 Cl 2 , CHCl 2 CHCl 2 , THF, DMF and DMSO, presumably due to aggregation caused by intermolecular hydrogen bonding at the cyclic imide moieties.…”

Synthesis of a platinacycle: determination of the structure and examination of the photophysical properties based on DFT calculations

“…The manner of aggregation is controllable with solvent media, leading to tuning of near-IR emission and vapochromism. 12 We have reported a series of Pt-containing polymers and examined their properties, including absorption-emission control by arylene moieties 14 and phosphine ligands, 15 triplet-triplet annihilation upconversion, 16 catalytic activity for hydrosilylation, 17 formation of chirally regulated structures based on chiral amide susbsituents 18,19 and phosphine ligands. [20][21][22] We have synthesized polymers bearing Pt-bipyridine bis(acetylide) complex moieties in the main chain by dehydrochlorination coupling polymerization of Pt-bipyridine dichlorides and bisethynylarylenes.…”