3d-d Excited States of Ni(II) Complexes Relevant to Photoredox Catalysis: Spectroscopic Identification and Mechanistic Implications.

Synthetic organic chemistry has seen major advances due to the merger of nickel and photoredox catalysis. A growing number of Ni-photoredox reactions are proposed to involve generation of excited nickel species, sometimes even in the absence of a photoredox catalyst. To gain insights about these excited states, two of our groups previously studied the photophysics of Ni(t-Bubpy)(o-Tol)Cl, which is representative of proposed intermediates in many Ni-photoredox reactions. This complex was found to have a long-lived excited state (τ = 4 ns), which was computationally assigned as a metal-to-ligand charge transfer (MLCT) state with an energy of 1.6 eV (38 kcal/mol). This work evaluates the computational assignment experimentally using a series of related complexes. Ultrafast UV-Vis and mid-IR transient absorption data suggest that a MLCT state is generated initially upon excitation but decays to a long-lived state that is 3d-d rather than 3MLCT in character. Dynamic cis,trans-isomerization of the square planar complexes was observed in the dark using 1H NMR techniques, supporting that this 3d-d state is tetrahedral and accessible at ambient temperature. Through a combination of transient absorption and NMR studies, the 3d-d state was determined to lie ∼0.5 eV (12 kcal/mol) above the ground state. Because the 3d-d state features a weak Ni-aryl bond, the excited Ni(II) complexes can undergo Ni homolysis to generate aryl radicals and Ni(I), both of which are supported experimentally. Thus, photoinduced Ni-aryl homolysis offers a novel mechanism of initiating catalysis by Ni(I).

Excited-State Switching between Ligand-Centered and Charge Transfer Modulated by Metal-Carbon Bonds in Cyclopentadienyl Iridium Complexes.

Three series of pentamethylcyclopentadienyl (Cp*) Ir(III) complexes with different bidentate ligands were synthesized and structurally characterized, [Cp*Ir(tpy)L] n+ (tpy = 2-tolylpyridinato; n = 0 or 1), [Cp*Ir(piq)L] n+ (piq = 1-phenylisoquinolinato; n = 0 or 1), and [Cp*Ir(bpy)L] m+ (bpy = 2,2'-bipyridine; m = 1 or 2), featuring a range of monodentate carbon-donor ligands within each series [L = 2,6-dimethylphenylisocyanide; 3,5-dimethylimidazol-2-ylidene (NHC); methyl)]. The spectroscopic and photophysical properties of these molecules and those of the photocatalyst [Cp*Ir(bpy)H]+ were examined to establish electronic structure-photophysical property relationships that engender productive photochemical reactivity of this hydride and its methyl analogue. The Ir(III) chromophores containing ancillary CNAr ligands exhibited features anticipated for predominantly ligand-centered (LC) excited states, and analogues bearing the NHC ancillary exhibited properties consistent with LC excited states containing a small admixture of metal-to-ligand charge-transfer (MLCT) character. However, the molecules featuring anionic and strongly σ-donating methyl or hydride ligands exhibited photophysical properties consistent with a high degree of CT character. Density functional theory calculations suggest that the lowest energy triplet states in these complexes are composed of a mixture of MLCT and ligand-to-ligand CT originating from both the Cp* and methyl or hydride ancillary ligands. The high degree of CT character in the triplet excited states of methyliridium complexes bearing C^N-cyclometalated ligands offer a striking contrast to the photophysical properties of pseudo-octahedral structures fac-Ir(C^N)3 or Ir(C^N)2(acac) that have lowest-energy triplet excited states characterized as primarily LC character with a more moderate MLCT admixture.

Ultrafast Dynamics of the Metal-to-Ligand Charge Transfer Excited States of Ir(III) Proteo and Deutero Dihydrides.

For decades, transition metal hydrides have been at the forefront of numerous photocatalytic reactions leveraging either photoacid or photohydride generation. Of upmost importance is the nature of the M-H bond itself, which is typically the major site of photochemical reactivity, particularly in Ir(III) hydrides featuring metal-to-ligand charge transfer (MLCT) excited states. As a departure point for understanding the fundamental spectroscopy and photophysics of the MLCT excited states of Ir(III) diimine hydrides, cis-[Ir(bpy)2H2]+ (bpy = 2,2'-bipyridine) and its deuterated analogue cis-[Ir(bpy)2D2]+ were prepared and investigated. The robust nature of these molecules enabled detailed solution-based photophysical studies using ultrafast transient absorption and infrared spectroscopy, executed without the generation of permanent photoproducts. Static Fourier transform infrared and Raman spectra (λex = 785 nm) of these two molecules revealed weak but measurable Ir-H and Ir-D stretching vibrations centered at 2120 and 1510 cm-1, respectively. Short-lived (τ = 25 ps) MLCT excited states were observed for both cis-[Ir(bpy)2H2]+ and cis-[Ir(bpy)2D2]+ following femtosecond pulsed laser excitation at 480 nm in visible and near-IR transient absorption experiments. A similar time constant was measured for the in-phase and out-of-phase Ir-H stretching modes of the triplet excited state between 1900 and 2200 cm-1 using transient IR spectroscopy. The Ir-D stretching modes in the MLCT excited state were masked by bpy-localized vibrations rendering quantitative evaluation of these modes difficult. The time-resolved infrared data were consistent with density functional theory calculated mid-IR difference spectra in both of these molecules, yielding quantitative matches to the measured IR difference spectra. The information presented here provides valuable insight for understanding the primary photophysical events and transient absorption and IR spectroscopic signatures likely to be encountered throughout metal hydride photochemistry.

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

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.

Photophysics and ultrafast processes in rhenium(I) diimine dicarbonyls.

In this work, a series of nine Re(i) diimine dicarbonyl complexes of the general molecular formula cis-[Re(N^N)2(CO)2]+ (N^N are various 2,2'-bipyridine (bpy) or 1,10-phenanthroline (phen) derivatives) were prepared and spectroscopically investigated to systematically evaluate the photophysical consequences of various substituents resident on the diimine ligands. These panchromatic absorbing chromophores were structurally characterized, evaluated for their electrochemical and spectroelectrochemical properties, and investigated using static and dynamic electronic absorption, photoluminescence (PL), and infrared spectroscopy from ultrafast to supra-nanosecond time scales. The ultrafast time-resolved infrared (TRIR) analysis was further supported by electronic structure calculations which characterized the changes within the two C[triple bond, length as m-dash]O vibrational modes upon formation of the metal-to-ligand charge transfer (MLCT) excited state. The MLCT excited state decay of this series of dicarbonyl molecules appears completely consistent with energy-gap law behavior, where the nonradiative decay rate constants increase logarithmically with decreasing excited state - ground state energy separation, except in anticipated cases where the substituents were phenyl or tert-butyl.

Bathophenanthroline Disulfonate Ligand-Induced Self-Assembly of Ir(III) Complexes in Water: An Intriguing Class of Photoluminescent Soft Materials.

Strong evidence of concentration-induced and dissolved electrolyte-induced chromophore aggregation has been universally observed in numerous water soluble bis-cyclometalated Ir(III) photosensitizers bearing the sulfonated diimine ligands bathophenanthroline disulfonate and bathocuproine disulfonate. This new class of aqueous-based soft materials was highly photoluminescent in their aggregated state where detailed spectroscopic investigations of this phenomenon revealed significant blue shifts of their respective photoluminescence emission spectra with concomitant increases in excited-state lifetimes and quantum yields initiating even at micromolar chromophore concentrations in water or upon the addition of a strong electrolyte. A combination of nanoscale particle characterization techniques, static and dynamic photoluminescence spectroscopic studies, along with atomistic molecular dynamics (MD) simulations of these soft materials suggests the formation of small, heterogeneous nanoaggregate structures, wherein the sulfonated diimine ancillary ligand serves as a pro-aggregating subunit in all instances. Importantly, the experimental and MD findings suggest the likelihood of discovering similar aqueous aggregation phenomena occurring in all transition-metal complexes bearing these water-solubilizing diimine ligands.