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

Dinuclear d 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)], where C^N is either 2-phenylpyridine (1) or 7,8-benzoquinoline (2), triplet ligand-centered (LC) photophysics results echoing that in a mononuclear model chromophore, [Pt(8HQ)] (3). The lengthened Pt-Pt distances of 3.

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.

d-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(bpy)(-Tol)Cl, which is representative of proposed intermediates in many Ni-photoredox reactions.

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.

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] (tpy = 2-tolylpyridinato; n = 0 or 1), [Cp*Ir(piq)L] (piq = 1-phenylisoquinolinato; n = 0 or 1), and [Cp*Ir(bpy)L] (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.

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)H] (bpy = 2,2'-bipyridine) and its deuterated analogue cis-[Ir(bpy)D] were prepared and investigated.