Ultrafast dynamics of 2E state formation in Cr(acac)3

Femtosecond time-resolved absorption spectroscopy has been used to elucidate the excited-state dynamics associated with formation of the (2)E excited state in a Cr(III) transition metal complex. Cr(acac)(3) (where acac is the deprotonated monoanion of acetylacetone) exhibits monophasic decay kinetics with tau = 1.1 +/- 0.1 ps following excitation into the lowest-energy ligand-field absorption band; the time constant is found to be independent of both excitation and probe wavelength across the entire (4)A(2) --> (4)T(2) absorption envelope. The lack of a significant shift in the excited-state absorption spectrum combined with the observed spectral narrowing is consistent with an assignment of this process as vibrational cooling (k(vib)) in the (2)E state. The data on Cr(acac)(3) indicate that intersystem crossing associated with the (4)T(2) --> (2)E conversion occurs at a rate k(ISC) > 10(13) s(-)(1) and furthermore competes effectively with vibrational relaxation in the initially formed (4)T(2) state. Excitation into the higher energy (4)LMCT state (lambda(ex) = 336 nm) gives rise to biphasic kinetics with tau( 1) = 50 +/- 20 fs and tau( 2) = 1.2 +/- 0.2 ps. The slower component is again assigned to vibrational cooling in the (2)E state, whereas the subpicosecond process is attributed to conversion from the charge-transfer to the ligand-field manifold. In addition to detailing a process central to the photophysics of Cr(III), these results reinforce the notion that the conventional picture of excited-state dynamics in which k(vib) > k(IC) > k(ISC) does not generally apply when describing excited-state formation in transition metal complexes.     

Excited-state equilibration over 30 A in a platinum(II) quinolinolate-bridge-platinum(II) porphyrin complex

Long-range triplet excited-state equilibration occurs over a nanometric distance between platinum(II) 8-quinolinolate (3Ptq2 = 1.87 eV) and platinum(II) tetraphenylporphyrin (3PtTPP = 1.89 eV). The equilibrium is mediated by a fluorene-thiophene-fluorene bridge (3FTF = 1.92 eV) and is characterized by a double-exponential decay (tau1 = 39 +/- 4 ps; tau2 = 351 +/- 15 ps) that suggests the participation of three separate excited states: 3Ptq2, 3FTF, and 3PtTPP, respectively. Numerical simulation of the dual equilibrium allowed for estimation of the individual rate constants for each of the reversible steps (kET = 3.9 x 10(9)-4.1 x 10(10) s(-1)). As a result of rapid triplet-state equilibration, almost 50% of the excited-state energy is directed from the PtTPP chromophore toward Ptq2, in spite of a small endothermic barrier (0.03 eV).     

Vibrational energy flow rates for cis- and trans-stilbene isomers in solution

Transient electronic absorption following excitation of the first C-H stretching overtone (2nu(CH)) or a C-H stretch-bend combination (nu(CH) + nu(bend)) monitors the flow of vibrational energy in cis-stilbene and in trans-stilbene. Following a rapid initial rise as energy flows into states interrogated by the probe pulse, the absorption decays with two time constants, which are about a factor of 2 longer for the cis-isomer than for the trans-isomer. The decay times for cis-stilbene are tau2(cis) = (2.6 +/- 1.5) ps and tau3(cis) = (24.1 +/- 2.1) ps, and those for trans-stilbene are tau2(trans) = (1.4 +/- 0.6) ps and tau3(trans) = (10.2 +/- 1.1) ps. The decay times are essentially the same in different solvents, suggesting that the relaxation is primarily intramolecular. The two decay times are consistent with the sequential flow of energy through sets of coupled states within the molecule, and the difference in the rates for the two isomers likely reflects differences in coupling among the states arising from the different structures of the isomers. The similarity of the time evolution following excitation of the first C-H overtone at 5990 cm(-1) and the stretch-bend combination at 4650 cm(-1) is consistent with a subset of states, whose structure is similar for the two vibrational excitation energies, controlling the observed flow of energy.     

Sub-picosecond mid-infrared spectroscopy of phytochrome Agp1 from Agrobacterium tumefaciens.

The photoinduced primary reaction of the biliverdin binding phytochrome Agp1 (Agp1-BV) from Agrobacterium tumefaciens was investigated by sub-picosecond time-resolved Vis pump-IR probe spectroscopy. Three time constants of tau(1)=0.7+/-0.05 ps, tau(2)=3.3+/-0.2 ps and tau(3)=33.3+/-1.5 ps could be isolated from the dynamics of structurally specific marker bands of the BV chromophore. These results together with those of accompanying sub-picosecond Vis pump-Vis probe spectroscopy allow the extension of the reaction scheme for the primary process by a vibrationally excited electronic ground state. The isomerization at the C15=C16 bond occurs within the lifetime of the excited electronic state. A quantum yield of 0.094 for the primary reaction is determined, suggesting that the quantum yield of formation of the P(fr) far-red-absorbing form is already established in the primary photoreaction of the P(r) (red-absorbing) form.     

Photoinduced electron transfer of N-[(3- and 4-diarylamino)phenyl]-1,8-naphthalimide dyads: orbital-orthogonal approach in a short-linked D-A system

The photoinduced electron transfer of a series of meta- and para-linked triphenylamine-naphthalimide dyads, N-{3- and 4-[bis(4-R-substituted phenyl)amino]phenyl}-1,8-naphthalimide, 1m,p (R = H), 2m,p (R = Me), 3m,p (R = OMe), and 4m,p (R = NMe2) was investigated in toluene and DMF. The singlet charge-transfer (CT) states were observed in all cases. The decay rates were found to be faster in DMF (tau = 6.5 ps to 100 ps) than those in toluene (tau = 190 ps to 7 ns). The long-lived triplet CT states were observed in toluene for 3 (ca. 10% contribution, tau = 670 ns for 3m, 240 ns for 3p). No long-lived species were detected in DMF. The decay rates were somewhat faster in the para-isomers than in the meta-isomers in most cases. The photolysis of 5 (p-phenylene extended analogue of 3, R = OMe) gave a singlet CT state and a locally excited triplet state on the naphthalimide chromophore.     

Intramolecular energy hopping and energy trapping in polyphenylene dendrimers with multiple peryleneimide donor chromophores and a terryleneimide acceptor trap chromophore

Intramolecular F?rster-type excitation energy transfer (FRET) processes in a series of first-generation polyphenylene dendrimers substituted with spatially well-separated peryleneimide chromophores and a terryleneimide energy-trapping chromophore at the rim were investigated by steady-state and time-resolved fluorescence spectroscopy. Energy-hopping processes among the peryleneimide chromophores are revealed by anisotropy decay times of 50--80 ps consistent with a FRET rate constant of k(hopp) = 4.6 ns(-1). If a terryleneimide chromophore is present at the rim of the dendrimer together with three peryleneimide chromophores, more than 95% of the energy harvested by the peryleneimide chromophores is transferred and trapped in the terryleneimide. The two decay times (tau(1) = 52 ps and tau(2) = 175 ps) found for the peryleneimide emission band are recovered as rise times at the terryleneimide emission band proving that the energy trapping of peryleneimide excitation energy by the terryleneimide acceptor occurs via two different, efficient pathways. Molecular- modeling-based structures tentatively indicate that the rotation of the terryleneimide acceptor group can lead to a much smaller distance to a single donor chromophore, which could explain the occurrence of two energy-trapping rate constants. All energy-transfer processes are quantitatively describable with F?rster energy transfer theory, and the influence of the dipole orientation factor in the F?rster equation is discussed.     

Transient lens spectroscopy of ultrafast internal conversion processes in citranaxanthin

The ultrafast internal conversion (IC) dynamics of the apocarotenoid citranaxanthin have been studied for the first time by means of two-color transient lens (TL) pump-probe spectroscopy. After excitation into the high-energy edge of the S2 band by a pump pulse at 400 nm, the subsequent intramolecular processes were probed at 800 nm. Experiments were performed in a variety of solvents at room temperature. Upper limits for the S2 lifetime tau2 on the order of 100-200 fs are estimated. The S1 lifetime tau1 varies only slightly between solvents (10-12 ps), and the only clear decrease is observed for methanol (8.5 ps). The findings are consistent with earlier results from transient absorption studies of other apocarotenoids and carotenoid ketones and transient lens experiments of C40 carbonyl carotenoids. Possible reasons for the observed weak solvent dependence of tau1 for citranaxanthin are discussed.     

Combining light-harvesting and charge separation in a self-assembled artificial photosynthetic system based on perylenediimide chromophores

Self-assembly of robust perylenediimide chromophores is used to produce an artificial light-harvesting antenna structure that in turn induces self-assembly of a functional special pair that undergoes ultrafast, quantitative charge separation. The structure consists of four 1,7-(3',5'-di-tert-butylphenoxy)perylene-3,4:9,10-perylene-3,4:9,10-bis(carboximide) (PDI) molecules attached to a single 1,7-bis(pyrrolidin-1-yl)perylene-3,4:9,10-perylene-3,4:9,10-bis(carboximide) (5PDI) core, which self-assembles to form (5PDI-PDI4)2 in toluene. The system is characterized using both structural methods (NMR, SAXS, mass spectroscopy, and GPC) and photophysical methods (UV-vis, time-resolved fluorescence, and femtosecond transient absorption spectroscopy). Energy transfer from (PDI)2 to (5PDI)2 occurs with tau = 21 ps, followed by excited-state symmetry breaking of 1*(5PDI)2 to produce 5PDI*+-5PDI*- quantitatively with tau = 7 ps. The ion pair recombines with tau = 420 ps. Electron transfer occurs only in the dimeric system and does not occur in the disassembled monomer, thus mimicking both antenna and special pair function in photosynthesis.     

Formation of the early photoproduct lumi-R of cyanobacterial phytochrome cph1 observed by ultrafast mid-infrared spectroscopy

The photoreactions of the Pr ground state of cyanobacterial phytochrome Cph1 from Synechocystis PCC 6803 have been investigated by picosecond time-resolved mid-infrared spectroscopy at ambient temperature. With femtosecond excitation of the Pr state at 640 nm, the photoisomerized Lumi-R product state is generated with kinetics and associated difference spectra indicative of vibrational cooling with tau(1) = 3 ps time constant and excited state decay with tau(1) = 3 ps, tau(2) = 14 ps, and tau(3) = 134 ps time constants. The Lumi-R state is characterized by downshifted absorption of three C=C modes assigned to C(15)=C(16), C(4)=C(6), and a delocalized C=C mode, in addition to the downshifted C(19)=O mode. The Lumi-R minus Pr difference spectrum is indicative of global restructuring of the chromophore on the ultrafast timescale, which is discussed in light of C(15) Z/E photoisomerization in addition to changes near C(5), which could be low bond order torsional angle changes.     

Wavelength-dependent electron and energy transfer pathways in a side-to-face ruthenium porphyrin/perylene bisimide assembly

A new side-to-face supramolecular array of chromophores, where a pyridyl-substituted perylene bisimide dye axially binds to two ruthenium porphyrin fragments, has been prepared by self-assembly. The array is formulated as DPyPBI[Ru(TPP)(CO)](2), where DPyPBI = N,N'-di(4-pyridyl)-1,6,7,12-tetra(4-tert-butylphenoxy)perylene-3,4:9,10-tetracarboxylic acid bisimide and TPP = 5,10,15,20-tetraphenylporphyrin. The photophysical behavior of DPyPBI[Ru(TPP)(CO)](2) has been studied by fast (nanoseconds) and ultrafast (femtoseconds) time-resolved techniques. The observed behavior sharply changes with excitation wavelength, depending on whether the DPyPBI or Ru(TPP)(CO) units are excited. After DPyPBI excitation, the strong fluorescence typical of this unit is completely quenched, and time-resolved spectroscopy reveals the occurrence of photoinduced electron transfer from the ruthenium porphyrin to the perylene bisimide dye (tau = 5.6 ps) followed by charge recombination (tau = 270 ps). Upon excitation of the Ru(TPP)(CO) fragments, on the other hand, ultrafast (tau < 1 ps) intersystem crossing is followed by triplet energy transfer from the ruthenium porphyrin to the perylene bisimide dye (tau = 720 ps). The perylene-based triplet state decays to the ground state on a longer time scale (tau = 9.8 micros). The photophysics of this supramolecular array provides remarkable examples of (i) wavelength-dependent behavior (a small change in excitation wavelength causes a sharp switch from electron to energy transfer) and (ii) intramolecular sensitization (the triplet state of the perylene bisimide, inaccessible in the free dye, is efficiently populated in the array).     

Ferroelectric domains in nitrobenzene-nitromethane solutions measured by hyper-Rayleigh scattering

Hyper-Rayleigh scattering (HRS) spectra were measured for liquid solutions of C6H5NO2 and CH3NO2 at T=300 K. The depolarized HRS spectra at small frequency shift are dominated by two components due to reorientation of the nitrobenzene molecules. One is a Lorentzian with spectral width nu1=0.16-0.45 cm(-1) and corresponding orientation relaxation time tau=33-12 ps. The second component is a narrow spike with spectral width <2 MHz and corresponding relaxation time tau>80 ns, attributed to HRS from slowly relaxing ferroelectric domains. The dipole order parameter g0=0.053+/-0.005, saturation parameter p=0.9+/-0.1, and volume V=20+/-6 nm3 for these domains in nitromethane were determined from measurements of the nitrobenzene-concentration dependence of the intensity ratio for these two spectral components. Orientation of the 230 nitromethane molecules within each domain is inhomogenous but highly ordered.     

Comprehensive investigation of vibrational relaxation of non-hydrogen-bonded water molecules in liquids

The vibrational dynamics of isolated water molecules dissolved in the nonpolar organic liquids 1,2-dichloroethane (C(2)H(4)Cl(2)) and d-chloroform (CDCl(3)) have been studied using an IR pump-probe experiment with approximately 2 ps time resolution. Analyzing transient, time, and spectrally resolved data in both the OH bending and the OH stretching region, the anharmonic constants of the bending overtone (v=2) and the bend-stretch combination modes were obtained. Based on this knowledge, the relaxation pathways of single water molecules were disentangled comprehensively, proving that the vibrational energy of H(2)O molecules is relaxing following the scheme OH stretch-->OH bend overtone-->OH bend-->ground state. A lifetime of 4.8+/-0.4 ps is determined for the OH bending mode of H(2)O in 1,2-dichloroethane. For H(2)O in CDCl(3) a numerical analysis based on rate equations suggests a bending overtone lifetime of tau(020)=13+/-5 ps. The work also shows that full 2-dimensional (pump-probe) spectral resolution with access to all vibrational modes of a molecule is required for the comprehensive analysis of vibrational energy relaxation in liquids.     

Solvation dynamics in ionic liquid swollen p123 triblock copolymer micelle: a femtosecond excitation wavelength dependence study

Femtosecond solvation dynamics of coumarin 480 (C480) in a mixed micelle is reported. The mixed micelle consists of a triblock copolymer (PEO)20-(PPO) 70-(PEO)20 (Pluronic P123) and an ionic liquid (IL), 1-pentyl-3-methylimidazolium tetrafluoroborate ([pmim][BF4]). At a low concentration (0.3 M), the sparingly water soluble IL ([pmim][BF4]) penetrates the hydrophobic PPO core of the P123 micelles. Thus emission maximum of C480 in the core (accessed at lambdaex=375 nm) in 0.3 M IL is red-shifted by 8 nm from that in its absence and the red edge excitation shift (REES) is large (19+/-1 nm). At a high concentration (0.9 M), the ionic liquid [pmim][BF4] invades both the core and corona region and the mixed micelle exhibits very small REES (3+/-1 nm). Anisotropy decay and solvation dynamics in different regions of the mixed micelle are studied by variation of excitation wavelength (lambda ex). In P123 micelle, the average rotational time () is 2800 ps in the core (at lambdaex=375 nm) and 1350 ps in the corona region (at lambdaex=435 nm). In 0.3 M [pmim][BF4], tau rot at the core of the mixed micelle decreases to 1950 ps while that in the corona remains unaffected. In 0.9 M IL, both the core and corona (lambda ex=375 and 435 nm) exhibit similar and short approximately 600 ps. In 0.3 M IL, solvation dynamics in the core region (lambdaex=375 nm) of P123 micelle is about 2 times faster than in its absence. In 0.3 M IL, solvation dynamics in the corona region (lambdaex=435 nm) is approximately 100 times faster than that in the core. In 0.9 M IL, the solvation dynamics in the core and in the corona is, respectively, approximately 9 times and 4 times faster than that in 0.3 M IL.     

Distinguishing between Dexter and rapid sequential electron transfer in covalently linked donor-acceptor assemblies

The syntheses, physical, and photophysical properties of a family of complexes having the general formula [M2(L)(mcb)(Ru(4,4'-(X)2-bpy)2)](PF6)3 (where M = Mn(II) or Zn(II), X = CH3 or CF3, mcb is 4'-methyl-4-carboxy-2,2'-bipyridine, and L is a Schiff base macrocycle derived from 2,6-diformyl-4-methylphenol and bis(2-aminoethyl)-N-methylamine) are described. The isostructural molecules all consist of dinuclear metal cores covalently linked to a Ru(II) polypyridyl complex. Photoexcitation of [Mn2(L)(mcb)(Ru((CF3)2-bpy)2)](PF6)3 (4) in deoxygenated CH2Cl2 solution results in emission characteristic of the 3MLCT excited state of the Ru(II) chromophore but with a lifetime (tau(obs) = 5.0 +/- 0.1 ns) and radiative quantum yield (Phi(r) approximately 7 x 10(-4)) that are significantly attenuated relative to the Zn(II) model complex [Zn2(L)(mcb)(Ru((CF3)2-bpy)2)](PF6)3 (6) (tau(obs) = 730 +/- 30 ns and Phi(r) = 0.024, respectively). Quenching of the 3MLCT excited state is even more extensive in the case of [Mn2(L)(mcb)(Ru((CH3)2-bpy)2)](PF6)3 (3), whose measured lifetime (tau(obs) = 45 +/- 5 ps) is >10(4) shorter than the corresponding model complex [Zn2(L)(mcb)(Ru((CH3)2-bpy)2)](PF6)3 (5) (tau(obs) = 1.31 +/- 0.05 micros). Time-resolved absorption measurements on both Mn-containing complexes at room-temperature revealed kinetics that were independent of probe wavelength; no spectroscopic signatures for electron-transfer photoproducts were observed. Time-resolved emission data for complex 4 acquired in CH2Cl2 solution over a range of 200-300 K could be fit to an expression of the form k(nr) = k0 + A x exp{-DeltaE/kB T} with k0 = 1.065 +/- 0.05 x 10(7) s(-1), A = 3.7 +/- 0.5 x 10(10) s(-1), and DeltaE = 1230 +/- 30 cm(-1). Assuming an electron-transfer mechanism, the variable-temperature data on complex 4 would require a reorganization energy of lambda approximately 0.4-0.5 eV which is too small to be associated with charge separation in this system. This result coupled with the lack of enhanced emission at temperatures below the glass-to-fluid transition of the solvent and the absence of visible absorption features associated with the Mn(II)2 core allows for a definitive assignment of Dexter transfer as the dominant excited-state reaction pathway. A similar conclusion was reached for complex 3 based in part on the smaller driving force for electron transfer (DeltaG0(ET) = -0.1 eV), the increase in probability of Dexter transfer due to the closer proximity of the donor excited state to the dimanganese acceptor, and a lack of emission from the compound upon formation of an optical glass at 80 K. Electronic coupling constants for Dexter transfer were determined to be approximately 10 cm(-1) and approximately 0.15 cm(-1) in complexes 3 and 4, respectively, indicating that the change in spatial localization of the excited state from the bridge (complex 3) to the periphery of the chromophore (complex 4) results in a decrease in electronic coupling to the dimanganese core of nearly 2 orders of magnitude. In addition to providing insight into the influence of donor/acceptor proximity on exchange energy transfer, this study underscores the utility of variable-temperature measurements in cases where Dexter and electron-transfer mechanisms can lead to indistinguishable spectroscopic observables.     

Photodecarbonylation of alpha-diketones: a mechanistic study of reactions leading to acenes

Poly(acene)s are significant compounds for various electronic applications. A clean, one-step synthesis involves alpha-diketones (2-4), which undergo facile Strating-Zwanenburg photodecarbonylation producing the corresponding poly(acene)s (i.e., anthracene, hexacene, and heptacene, respectively). Compounds 2-4 show weak fluorescence (lambdaF=approximately 525-530 nm and PhiF=approximately 0.1-0.4%) and phosphorescence (lambdaPh=approximately 565-570 nm) and have a small singlet-triplet energy gap (S1-T1 gap, approximately 4 kcal/mol) that facilitates rapid intersystem crossing from the singlet to the triplet state. Both the singlet states (tauS=approximately 20-218 ps) and the triplet states (tauT=approximately 370 ps to <7 ns) of 2-4 are short-lived, while the decarbonylation of 2-4 is a rapid process occurring within 7 ns from both the singlet and the triplet manifolds. The nanosecond laser flash photolysis of 4 also reveals the T-T absorption of heptacene (580 nm, tau=approximately 11 micros).     

The interaction of MS-325 with human serum albumin and its effect on proton relaxation rates

MS-325 is a novel blood pool contrast agent for magnetic resonance imaging currently undergoing clinical trials to assess blockage in arteries. MS-325 functions by binding to human serum albumin (HSA) in plasma. Binding to HSA serves to prolong plasma half-life, retain the agent in the blood pool, and increase the relaxation rate of water protons in plasma. Ultrafiltration studies with a 5 kDa molecular weight cutoff filter show that MS-325 binds to HSA with stepwise stoichiometric affinity constants (mM(-1)) of K(a1) = 11.0 +/- 2.7, K(a2) = 0.84 +/- 0.16, K(a3) = 0.26 +/- 0.14, and K(a4) = 0.43 +/- 0.24. Under the conditions 0.1 mM MS-325, 4.5% HSA, pH 7.4 (phosphate-buffered saline), and 37 degrees C, 88 +/- 2% of MS-325 is bound to albumin. Fluorescent probe displacement studies show that MS-325 can displace dansyl sarcosine and dansyl-L-asparagine from HSA with inhibition constants (K(i)) of 85 +/- 3 microM and 1500 +/- 850 microM, respectively; however, MS-325 is unable to displace warfarin. These results suggest that MS-325 binds primarily to site II on HSA. The relaxivity of MS-325 when bound to HSA is shown to be site dependent. The Eu(III) analogue of MS-325 is shown to contain one inner-sphere water molecule in the presence and in the absence of HSA. The synthesis of an MS-325 analogue, 5, containing no inner-sphere water molecules is described. Compound 5 is used to estimate the contribution to relaxivity from the outer-sphere water molecules surrounding MS-325. The high relaxivity of MS-325 bound to HSA is primarily because of a 60-100-fold increase in the rotational correlation time of the molecule upon binding (tau(R) = 10.1 +/- 2.6 ns bound vs 115 ps free). Analysis of the nuclear magnetic relaxation dispersion (T(1) and T(2)) profiles also suggests a decrease in the electronic relaxation rate (1/T(1e) at 20 MHz = 2.0 x 10(8) s(-1) bound vs 1.1 x 10(9) s(-1) free) and an increase in the inner-sphere water residency time (tau(m) = 170 +/- 40 ns bound vs 69 +/- 20 ns free).     

Ultrafast excited state dynamics of Pt(II) chromophores bearing multiple infrared absorbers

The paper reports the synthesis, structural characterization, electrochemistry, ultrafast time-resolved infrared (TRIR) and transient absorption (TA) spectroscopy associated with two independent d (8) square planar Pt(II) diimine chromophores, Pt(dnpebpy)Cl 2 ( 1) and Pt(dnpebpy)(C[triple bond]Cnaph) 2 ( 2), where dnpebpy = 4,4'-(CO 2CH 2- (t) Bu) 2-2,2'-bipyridine and CCnaph = naphthylacetylide. The neopentyl ester substitutions provided markedly improved complex solubility relative to the corresponding ethyl ester which facilitates synthetic elaboration as well as spectroscopic investigations. Following 400 nm pulsed laser excitation in CH 2Cl 2, the 23 cm (-1) red shift in the nu C=O vibrations in 1 are representative of a complex displaying a lowest charge-transfer-to-diimine (CT) excited state. The decay kinetics in 1 are composed of two time constants assigned to vibrational cooling of the (3)CT excited-state concomitant with its decay to the ground state (tau = 2.2 +/- 0.4 ps), and to cooling of the formed vibrationally hot ground electronic state (tau = 15.5 +/- 4.0 ps); we note that an assignment of the latter to a ligand field state cannot be excluded. Ultrafast TA data quantitatively support these assignments yielding an excited-state lifetime of 2.7 +/- 0.4 ps for the (3)CT excited-state of 1 and could not detect any longer-lived species. The primary intention of this study was to develop a Pt (II) complex ( 2) bearing dual infrared spectroscopic tags (C[triple bond]C attached to the metal and CO (ester) attached to the diimine ligand) to independently track the movement of charge density in different segments of the molecule following pulsed light excitation. Femtosecond laser excitation of 2 in CH 2Cl 2 at 400 nm simultaneously induces a red-shift in both the nu C=O (-30 cm (-1)) and the nu C[triple bond]C (-61 cm (-1)) vibrations. The TRIR data in 2 are consistent with a charge transfer assignment, and the significant decrease of the energy of the nu C[triple bond]C vibration suggests a considerable contribution from the acetylide ligands in the highest occupied molecular orbital. Therefore, we assign the lowest energy optical transitions in 2 as a combination of metal-to-ligand and ligand-to-ligand charge transfers. The excited-state of 2 is emissive at RT, with an emission maximum at 715 nm, quantum yield of 0.0012, and lifetime of 23 ns.     

Proton dynamics in lithium-ammonia solutions and expanded metals

Quasielastic neutron scattering has been used to study proton dynamics in the system lithium-ammonia at concentrations of 0, 4, 12, and 20 mole percent metal (MPM) in both the liquid and solid (expanded metal) phases. At 230 K, in the homogenous liquid state, we find that the proton self-diffusion coefficient first increases with metal concentration, from 5.6x10(-5) cm2 s(-1) in pure ammonia to 7.8x10(-5) cm2 s(-1) at 12 MPM. At higher concentrations we note a small decrease to a value of 7.0x10(-5) cm2 s(-1) at 20 MPM (saturation). These results are consistent with NMR data, and can be explained in terms of the competing influences of the electron and ion solvation. At saturation, the solution freezes to form a series of expanded metal compounds of composition Li(NH3)4. Above the melting point, at 100 K, we are able to fit our data to a jump-diffusion model, with a mean jump length (l) of 2.1 A and residence time (tau) of 3.1 ps. This model gives a diffusion coefficient of 2.3x10(-5) cm2 s(-1). In solid phase I (cubic, stable from 88.8 to 82.2 K) we find that the protons are still undergoing this jump diffusion, with l=2.0 A and tau=3.9 ps giving a diffusion coefficient of 1.8x10(-5) cm2 s(-1). Such motion gives way to purely localized rotation in solid phases IIa (from 82.2 to 69 K) and IIb (stable from 69 to 25 K). We find rotational correlation times (tau(rot)) of the order of 2.0 and 7.3 ps in phases IIa and IIb, respectively. These values can be compared with a rotational mode in solid ammonia with tau(rot) approximately 2.4 ps at 150 K.     

Effect of surface immobilization on intramolecular and intermolecular electron transfer in a chromophore-donor-acceptor assembly

A chromophore-donor-acceptor assembly [Ru(bpyCOOH)(bpyCH(2)MV(2+)) (bpyCH(2)PTZ)](4+)(1) (where bpyCOOH = 4-carboxylic acid-4'-methyl-2,2'-bipyridine, bpyCH(2)MV(2+) = 1-[(4'-methyl-2,2'-bipyridin-4-yl)methyl]-1'-methyl-4,4'-bipyridinediium, and bpyCH(2)PTZ = 10-[(4'-methyl-2,2'-bipyridin-4-yl)methyl]phenothiazine) has been adsorbed on the surface of nanocrystalline ZrO(2) and its excited state properties studied by emission and transient absorption spectroscopy. In deaerated acetonitrile solution, the complex emits weakly with an emission quantum yield of phi(em) approximately equal to 0.01 with an excited-state lifetime of tau approximately equal to 20 ps. Emission from the surface-adsorbed complex is intense, with phi(em) approximately equal to 0.4 and tau approximately equal to 40 ns. The increase in emission on the surface is likely due to a significant inhibition to the electron-transfer quenching of the metal-to-ligand charge transfer (MLCT) excited state caused by surface adsorption-induced changes in the redox potentials. Transient (nanosecond time scale) absorption monitoring, following laser flash photolysis, reveals the presence of a transient or transients that are formed during the flash. Transient spectral changes that occur during and after the flash are consistent with the formation and decay of the intermediate ZrO(2)-[Ru(bpyCOOH)(bpyCH(2)MV(+*))(bpyCH(2)PTZ(+*))](4+). It returns to the ground state by both intramolecular and intermolecular processes. Intramolecular electron transfer occurs with k(BET) = 6.3 x 10(6) s(-1) (tau = 160 ns), which is comparable to the rate constant for back-electron transfer in solution. The back-electron transfer is a second-order process and is much slower, with k(BET) = 390 M(-1) s(-1) (tau = 2.6 ms).