Effects of non-covalent interactions on the electronic and electrochemical properties of Cu(i) biquinoline complexes.

A Cu(i) complex {[CuI(biq)2]ClO4-biq} with biq = 2,2'-biquinoline was prepared, fully characterized and its properties compared with those of the well-known [CuI(biq)2]ClO4 complex. The crystal structures were obtained for both complexes (crystal structure for [CuI(biq)2]ClO4 has not been previously reported). Complex [CuI(biq)2]ClO4 crystallizes as a racemate where each enantiomer has a different τ4 value while compound {[CuI(biq)2]ClO4-biq} crystallizes as a non-chiral supramolecular aggregate with an uncoordinated biq molecule forming a π-π stacking interaction with a coordinated biq. 1H-NMR spectroscopy in non-coordinating solvents reveals that structures in solution are similar to those in the solid phase, confirming the presence of a supramolecular arrangement for compound {[CuI(biq)2]ClO4-biq}. The stability of the non-covalent aggregate in solution of {[CuI(biq)2]ClO4-biq} causes significant differences between the spectroscopic and electrochemical properties of {[CuI(biq)2]ClO4-biq} and [CuI(biq)2]ClO4.

Double heterojunction nanowire photocatalysts for hydrogen generation.

Charge separation and charge transfer across interfaces are key aspects in the design of efficient photocatalysts for solar energy conversion. In this study, we investigate the hydrogen generating capabilities and underlying photophysics of nanostructured photocatalysts based on CdSe nanowires (NWs). Systems studied include CdSe, CdSe/CdS core/shell nanowires and their Pt nanoparticle-decorated counterparts. Femtosecond transient differential absorption measurements reveal how semiconductor/semiconductor and metal/semiconductor heterojunctions affect the charge separation and hydrogen generation efficiencies of these hybrid photocatalysts. In turn, we unravel the role of surface passivation, charge separation at semiconductor interfaces and charge transfer to metal co-catalysts in determining photocatalytic H2 generation efficiencies. This allows us to rationalize why Pt nanoparticle decorated CdSe/CdS NWs, a double heterojunction system, performs best with H2 generation rates of ∼434.29 ± 27.40 µmol h(-1) g(-1) under UV/Visible irradiation. In particular, we conclude that the CdS shell of this double heterojunction system serves two purposes. The first is to passivate CdSe NW surface defects, leading to long-lived charges at the CdSe/CdS interface capable of carrying out reduction chemistries. Upon photoexcitation, we also find that CdS selectively injects charges into Pt NPs, enabling simultaneous reduction chemistries at the Pt NP/solvent interface. Pt nanoparticle decorated CdSe/CdS NWs thus enable reduction chemistries at not one, but rather two interfaces, taking advantage of each junction's optimal catalytic activities.

A single- and double-flash flash photolysis study of the sequential biphotonic photoprocesses of Cu(I) phenanthrolines. Comparison of the helicate complex, [Cu2(1,3-bis(9-methyl-1,10-phenanthrolin-2-yl)propane)2]2+, and [Cu(2,9-dimethyl-1,10-phenanthroline)2]+ photoprocesses.

Photochemical processes induced when two photons are sequentially absorbed by the helicate complex [Cu2(mphenpr)2](2+), where mphenpr = 1,3-bis(9-methyl-1,10-phenanthrolin-2-yl)propane, and [Cu(dmp)2](+) were investigated in CH2Cl2 containing solvents. A strong resemblance was observed between the fs-ns photophysics of [Cu2(mphenpr)2](2+) and Cu(I) phenanthroline complexes having a large steric hindrance. In the biphotonic regime, single-flash flash-photolyzed solutions were used for the determination of the product concentrations and quantum yields. The concentration of Cl(-) produced by the photoinduced decomposition of CH2Cl2 increases linearly with flash intensity as expected for a monophotonic process. In contrast, the concentration of a decomposed Cu(I) complex exhibits the quadratic dependence on flash intensity of a biphotonic process. Results of a sequential double-flash flash photolysis experiment are consistent with the decomposition of CH2Cl2 ahead of the flattened excited state formation and with the absorption of the second photon by the flattened MLCT excited state.

Unfolding of the [Cu2(1,3-bis(9-methyl-1,10-phenanthrolin-2-yl)propane)2]2+ helicate. Coupling of the chlorocarbon dehalogenation to the unfolding process.

A new helical dimeric copper(I) complex [Cu(2)(mphenpr)(2)](ClO(4))(2) where mphenpr is 1,3-bis(9-methyl-1,10-phenanthrolin-2-yl)propane has been prepared and characterized by X-ray crystallography and NMR. In the solid state, the metal centers are 6.42 A apart, and the electronic structure has been investigated with use of density functional theory (DFT) calculations. In solution the dimer equilibrates with a monomeric form [Cu(mphenpr)](ClO(4)), and the mechanism of unfolding of the dimer into monomer has been studied. In the presence of CCl(4), formation of the monomer is coupled to the reductive dehalogenation of the halocarbon. The mechanism of this process has been probed by the study of short-lived potential reaction intermediates using fast kinetic pulse radiolysis techniques and comparisons with DFT calculations. The copper(II) product [Cu(mphenpr)Cl](ClO(4)) and an analogue [Cu(mphenpr)](ClO(4))(2) have been isolated and characterized by X-ray crystallography.

Resonance energy transfer in the solution phase photophysics of -Re(CO)3 L+ pendants bonded to poly(4-vinylpyridine).

Polymers with general formula ([(vpy) 2vpyRe(CO) 3(tmphen) (+)]) n ([(vpy) 2vpyRe(CO) 3(NO 2-phen) (+)]) m (NO 2-phen = 5-nitro-1,10-phenanthroline; tmphen = 3,4,7,8-tetramethyl-1,10-phenanthroline); vpy = 4-vinylpyridine) were prepared and their morphologies were studied by transmission electron microscopy (TEM). Multiple morphologies of aggregates from these Re I polymers were obtained by using different solvents. Energy transfer between MLCT Re-->tmphen and MLCT Re-->NO 2 -phen excited states inside the polymers was evidenced by steady state and time-resolved spectroscopy. Current Forster resonance energy transfer theory was successfully applied to energy transfer processes in these polymers.

Intercalation of fac-[(4,4'-bpy)ReI(CO)3(dppz)]+, dppz = dipyridyl[3,2-a:2'3'-c]phenazine, in polynucleotides. On the UV-vis photophysics of the Re(I) intercalator and the redox reactions with pulse radiolysis-generated radicals.

The intercalation of fac-[(4,4'-bpy)Re(I)(CO)3(dppz)]+ (dppz = dipyridyl[3,2-a:2'3'-c]phenazine) in polynucleotides, poly[dAdT]2 and poly[dGdC]2, where A = adenine, G = guanine, C = cytosine and T = thymine, is a major cause of changes in the absorption and emission spectra of the complex. A strong complex-poly[dAdT]2 interaction drives the intercalation process, which has a binding constant, Kb approximately 1.8 x 10(5) M(-1). Pulse radiolysis was used for a study of the redox reactions of e(-)(aq), C*H(2)OH and N3* radicals with the intercalated complex. These radicals exhibited more affinity for the intercalated complex than for the bases. Ligand-radical complexes, fac-[(4,4'-bpy*)Re(I)(CO)3(dppz)] and fac-[(4,4'-bpy)Re(I)(CO)3(dppz *)], were produced by e(-)(aq) and C*H(2)OH, respectively. A Re(II) species, fac-[(4,4'-bpy)Re(II)(CO)3(dppz)](2+), was produced by N3* radicals. The rate of annihilation of the ligand-radical species was second order on the concentration of ligand-radical while the disappearance of the Re(II) complex induced the oxidative cleavage of the polynucleotide strand.

On the association and structure of radicals derived from dipyridil[3,2-a:2'3'-c]phenazine. Contrast between the electrochemical, radiolytic, and photochemical reduction processes.

The reduction of dipyridil[3,2-a:2'3'-c]phenazine, dppz, by pulse radiolytically generated e(-)(sol) or by the reaction of the dppz excited states with electron donors produces the radical dppzH(.). The dimer radical, (dppz)(2)H(.), exists in equilibrium with dppz with an association constant, K = 10(3) M(-1). The rate constant for the reaction of dppzH(.) with dppz is k = 4.3 x 10(6) M(-1) s(-1). DFT calculations on the structures of dppzH(.) and the doubly reduced and doubly protonated dppzH(2) rendered a planar structure for the former species and a bent one for the latter.

Contrasting intrastrand photoinduced processes in macromolecules containing pendant -Re(CO)3(1,10-phenanthroline)+: electron versus energy transfer.

The photochemical and photophysical properties of the polymers [(vpy-CH3+)2-vpyRe(CO)3(phen)+]200 (vpy = vinyl pyridine, phen = 1,10-phenanthroline) have been investigated in solution phase and compared to those of a related polymer, [(vpy)2-vpyRe(CO)3(phen)+]200, and monomer, pyRe(CO)3(phen)+. Irradiations at 350 nm induce intrastrand charge separation in the peralkylated polymer, a process that stands in contrast with the energy migration observed with [(vpy)(2)-vpyRe(CO)3(phen)+]200. Electronically excited -vpyRe(CO)3(phen)+ chromophores and charge-separated intermediates react with neutral species, e.g., 2,2',2' '-nitrilotriethanol, and anionic electron donors, e.g., SO3(2-) and I-. The anionic electron donors react more efficiently with the metal-to-ligand charge transfer excited state of these polyelectrolytes than with the excited state of pyRe(CO)3(phen)+.

On the adiabaticity contribution to the rate of outer-sphere electron transfers. Reactions of cytochrome c and related transition metal compounds.

Magnetokinetic effects were observed between 0 and 8 T in electron-transfer reactions of Ru(bipy)3(3+) with ferrous cytochrome c, Fe(bipy)3(2+), Fe(Me4-[14]1,3,8,10-tetraene-1,4,8,11-N4)(solvent)2(2+), and Ru(NH3)6(2+). The effects have been related to the adiabatic character of the reactions and rationalized in terms of a mechanism that incorporates the spin-orbit coupling, hyperfine-coupling, and Zeeman mechanism in the expression of the reaction rate constant.

Ultraviolet Photochemistry of Co(III)L(H(2)O)SO(3)(+) [L = Me(6)[14]dieneN(4), [14]aneN(4)] Complexes. Quandaries about the Linkage Isomerization to O-Bonded Sulfite and the Photogeneration of Cobalt(I) in Sequential Biphotonic Photolysis.

Two new macrocyclic complexes with S-bonded sulfite, Co(Me(6)[14]diene N(4))(H(2)O)SO(3)(+) and Co([14]ane N(4))(H(2)O)SO(3)(+), were prepared. The type of the SO(3)(2)(-) linkage in [Co(Me(6)[14]dieneN(4))(H(2)O)SO(3)]ClO(4) was established by means of the X-ray structure (crystal system, orthorhombic; space group, P2(1)2(1)2(1) (No. 19); a = 7.0342(8) Å, b = 14.696(2) Å, c = 23.302(5) Å). In a study of the photochemical properties, transient spectra revealed the photoredox formation of Co(II) macrocycles and the photoisomerization to O-bonded sulfite. Precursors of these products were also observed and tentatively identified a an ion pair (tau = 60 and 140 ns, respectively) and an adduct of the SO(3)(*)(-) radical and the unsaturated macrocycle Me(6)[14]diene N(4) (tau = 2.5 &mgr;s). The photogeneration of SO(3)(*)(-) was verified by means of the radical's ESR spectrum. High power laser irradiations resulted in the secondary photolysis of the intermediates and the formation of Co(I) products. The mechanism of the primary and secondary photolysis is discussed.

Charge-Transfer Processes in (4-Nitrobenzoate)Re(CO)(3)(azine)(2) Complexes. Competitive Reductions of 4-Nitrobenzoate and Azine in Thermally and Photochemically Induced Redox Processes.

The photochemically and thermally induced redox reactions of the (4-nitrobenzoate)Re(CO)(3) (azine) (azine = 1,10-phenanthroline, 2,2'-bipyridine, and (4-phenylpyridine)(2)) were investigated by flash photolysis and pulse radiolysis. Processes characterized as intramolecular charge transfers from coordinated azine radicals to the 4-nitrobenzoate ligand and vice versa were observed in a 1-100 &mgr;s time scale by pulse radiolysis. In photochemical experiments, the conversion among metal to ligand charge-transfer excited states, i.e., from the Re to azine to the Re to 4-nitrobenzoate charge-transfer excited state, involves intermediates with lives of picoseconds. A mechanism for the conversions that incorporates intraligand excited states is discussed.

Mechanism of (&mgr;-H)(&mgr;-alkenyl)Re(2)(CO)(8) Formation in 350 nm Flash Irradiations of Re(2)(CO)(10).

The mechanism of (&mgr;-H)(&mgr;-alkenyl)Re(2)(CO)(8) formation upon UV irradiations of Re(2)(CO)(10) in presence of olefin (styrene, trans-stilbene, 4-methyl-1-cyclohexane, and ethylene) was investigated by laser flash photolyses. Such photoproducts result from reactions of the olefin with eq-Re(2)(CO)(9). No reactions of Re(CO)(5) leading to hydride alkenyl products were observed. Dependences of the reaction rate on olefin concentration and solvent revealed an additional intermediate formed after the addition of the olefin to eq-Re(2)(CO)(9) and before the appearance of the &mgr;-hydrido-&mgr;-alkenyl products.

Electron-Transfer Reactions of Re(CO)(5): Atom-Transfer-Concerted Mechanism vs Bimetallic Intermediate Formation.

Flash photochemically generated Re(CO)(5) reacts with halide complexes, Cu(Me(4)[14]-1,3,8,10-tetraeneN(4))X(+), Cu(Me(2)pyo[14]trieneN(4))X(+), and Ni(Me(2)pyo[14]trieneN(4))X(+) (X = Cl, Br, I) and ion pairs, [Co(bipy)(3)(3+), X(-)]. The rate constants for the electron transfers have values, k approximately 10(9) M(-1) s(-1), close to expectations for processes with diffusion-controlled rates. Reaction intermediates, probably bimetallic species, were detected in electron-transfer reactions of Re(CO)(5) with Cu(Me(6)[14]dieneN(4))X(+), (X = Cl, Br, I). In the absence of the halides X(-), the electron-transfer reactions between Re(CO)(5) and these complexes are slow, k < 10(6) M(-1) s(-1). The results are discussed in terms of inner-sphere pathways, namely an atom-transfer-concerted mechanism. The mediation of bimetallic intermediates in the electron transfer is also considered.