Enhancing the photophysical properties of Ru(II) complexes by specific design of tridentate ligands

Rupp, Mira T.; Shevchenko, N. Ye.; Hanan, Garry S.; Kurth, Dirk G.

doi:10.1016/j.ccr.2021.214127

Cited by 31 publications

(26 citation statements)

References 66 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…For this reason, there is a long-lasting interest in the design of efficient molecular photosensitizers and photocatalysts. − Besides a sufficient (photo)stability and a reversible electrochemical behavior, these molecules should absorb in a wide range of visible light and possess long-lived excited states to enable subsequent chemical reactions. ,,, In addition to organic dyes, especially transition-metal complexes play a crucial role due to their advantageous properties and easy tunability. In fact, traditional noble metal complexes based on Ru(II), − Ir(III), − or Re(I) , have attracted much attention during the last decades and are still under constant development. However, the interest in complexes using more earth-abundant 3d metals such as Cr, − Fe, − Zn, , and Cu ,− is strongly increasing due to advantages in costs and availability.…”

Section: Introductionmentioning

confidence: 99%

Unexpected Boost in Activity of a Cu(I) Photosensitizer by Stabilizing a Transient Excited State

et al. 2022

View full text Add to dashboard Cite

In this study, we present a slight but surprisingly successful structural modification of the previously reported heteroleptic Cu(I) photosensitizer Cubiipo ([(xantphos)Cu(biipo)]PF6; biipo = 16H-benzo-[4′,5′]-isoquinolino-[2′,1′:1,2]-imidazo-[4,5-f]-[1,10]-phenanthrolin-16-one). As a key feature, biipo bears a naphthalimide unit at the back, which is directly fused to a phenanthroline moiety to extend the conjugated π-system. This ligand was now altered to include two additional methyl groups at the 2,9-positions at the phenanthroline scaffold. Comparing the novel Cudmbiipo complex to its predecessor, ultrafast transient absorption spectroscopy reveals the efficient suppression of a major deactivation pathway by stabilization of a transient triplet state. Furthermore, quantitative measurements of singlet oxygen evolution in solution confirmed that a larger fraction of the excited-state population is transferred to the photocatalytically active ligand-centered triplet 3LC state with a much longer lifetime of ∼30 μs compared to Cubiipo (2.6 μs). In addition, Cudmbiipo was compared with the well-established reference complex Cubcp ([(xantphos)Cu(bathocuproine)]PF6) in terms of its photophysical and photocatalytic properties by applying time-resolved femto- and nanosecond absorption, step-scan Fourier transform infrared (FTIR), and emission spectroscopies. Superior light-harvesting properties and a greatly enhanced excited-state lifetime with respect to Cubcp enable Cudmbiipo to be more active in exemplary photocatalytic applications, i.e., in the formation of singlet oxygen and the isomerization of (E)-stilbene.

show abstract

Section: Introductionmentioning

confidence: 99%

Unexpected Boost in Activity of a Cu(I) Photosensitizer by Stabilizing a Transient Excited State

et al. 2022

View full text Add to dashboard Cite

show abstract

“…2H;aromatic protons),7H;naphthyl protons and Ph),4H;naphthyl proton and Ph),2H;naphthyl protons),2H;aromatic protons),3H; aromatic protons and tpy (H6")), 6.08 (d, 3 J(H,H) = 8.8 Hz, 1H; Ph), 6.02 ppm (t, 3 J(H,H) = 8.6 Hz, 2H; Ph); 13 C{ 1 H} NMR (100.6 MHz, CD 2 Cl 2 , 25 °C): δ = 160.5 (s; tpy (C6)), 159.8 (s; ipso tpy (C2)), 159. 6 Chemistry-A European Journal…”

Section: Chemistry-a European Journalmentioning

confidence: 99%

“…[4] In this context, the non‐innocent redox‐active terpyridine (tpy) ligand has been used to obtain robust pincer complexes for catalysis and supramolecular chemistry. [5] Although the [Ru(tpy) 2 ]X 2 species show reduced photophysical properties compared to the related bpy derivatives, on account of the rigidity and narrow bite angle of the NNN ligand, [6] monodentate phosphines tpy complexes show attractive properties as near‐infrared sensitizers. [7] In addition to the use of a photosensitizer as single species or in combination with an additional catalyst (dual photoredox catalysis), a transition metal complex may also play a double role by harvesting photon energy and catalyzing bond breaking/forming reactions via a traditional or a new type of mechanism, avoiding the employment of an exogenous photosensitizer (visible light‐induced transition metal catalysis).…”

Section: Introductionmentioning

confidence: 99%

Terpyridine Diphosphine Ruthenium Complexes as Efficient Photocatalysts for the Transfer Hydrogenation of Carbonyl Compounds

Ballico

Alessi

Jandl

et al. 2022

Chemistry A European J

View full text Add to dashboard Cite

The cationic achiral and chiral terpyridine diphosphine ruthenium complexes [RuCl(PP)(tpy)]Cl (PP = dppp (1), (R,R)-Skewphos (2) and (S,S)-Skewphos (3)) are easily obtained in 85-88 % yield through a one-pot synthesis from [RuCl 2 (PPh 3 ) 3 ], the diphosphine and 2,2':6',2''-terpyridine (tpy) in 1-butanol. Treatment of 1-3 with NaPF 6 in methanol at RT affords quantitatively the corresponding derivatives [RuCl(PP)(tpy)]PF 6 (PP = dppp (1 a), (R,R)-Skewphos (2 a) and (S,S)-Skewphos (3 a)). Reaction of [RuCl 2 (PPh 3 ) 3 ] with (S,R)-Josiphos or (R)-BINAP in toluene, followed by treatment with tpy in 1-butanol and finally with NaPF 6 in MeOH gives [RuCl(PP)(tpy)]PF 6 (PP = (S,R)-Josiphos (4 a), (R)-BINAP (5 a))isolated in 78 % and 86 % yield, respectively. The chiral derivatives have been isolated as single stereoisomers and 3 a, 4 a have been characterized by single crystal X-ray diffraction studies. The tpy complexes with NaOiPr display high photocatalytic activity in the transfer hydrogenation (TH) of carbonyl compounds using 2-propanol as the only hydrogen donor and visible light at 30 °C, at remarkably high S/C (up to 5000) and TOF values up to 264 h À 1 . The chiral enantiomers 2, 2 a and 3, 3 a induce the asymmetric photocatalytic TH of acetophenone, affording (S)-and (R)-1-phenylethanol with 51 and 52 % ee, respectively, in a MeOH/2propanol mixture.

show abstract

“…The poor bite angle for the terpy ligands in Ruterpy essentially means that the ligand-field splitting is weaker when compared to the Rubipy complex. 18 The importance of this effect becomes very clear when discussing the relative energies of electronic states within the two complexes ( vide infra ).…”

Section: Basic Photophysics and Photorelease Mechanismmentioning

confidence: 99%

Recent advances in photorelease complexes for therapeutic applications

Benniston

Zeng

2022

Dalton Trans.

View full text Add to dashboard Cite

show abstract

Enhancing the photophysical properties of Ru(II) complexes by specific design of tridentate ligands

Cited by 31 publications

References 66 publications

Unexpected Boost in Activity of a Cu(I) Photosensitizer by Stabilizing a Transient Excited State

Unexpected Boost in Activity of a Cu(I) Photosensitizer by Stabilizing a Transient Excited State

Terpyridine Diphosphine Ruthenium Complexes as Efficient Photocatalysts for the Transfer Hydrogenation of Carbonyl Compounds

Recent advances in photorelease complexes for therapeutic applications

Contact Info

Product

Resources

About