Improving photocurrent generation: supramolecularly and covalently functionalized single-wall carbon nanotubes-polymer/porphyrin donor-acceptor nanohybrids

Novel nanohybrids based on covalently and noncovalently functionalized single-wall carbon nanotubes (SWNTs) have been prepared and assembled for the construction of photoactive electrodes. Polymer-grafted SWNTs were synthesized by free-radical polymerization of (vinylbenzyl)trimethylammonium chloride. Poly[(vinylbenzyl)trimethylammonium chloride] (PVBTAn+) was also noncovalently wrapped around SWNTs to form stable, positively charged SWNT/PVBTAn+ suspensions in water. Versatile donor-acceptor nanohybrids were prepared by using the electrostatic/van der Waals interactions between covalent SWNT-PVBTAn+ and/or noncovalent SWNT/PVBTAn+ and porphyrins (H2P8- and/or ZnP8-). Several spectroscopic, microscopic, transient, and photoelectrochemical measurements were taken to characterize the resulting supramolecular complexes. Photoexcitation of the nanohybrids afforded long-lived radical ion pairs with lifetimes as long as 2.2 micros. In the final part, photoactive electrodes were constructed by using a layer-by-layer technique on an indium tin oxide covered glass support. Photocurrent measurements gave remarkable internal photon-to-current efficiencies of 3.81 and 9.90 % for the covalent ZnP8-/SWNT-PVBTAn+ and noncovalent ZnP8-/SWNT/PVBTAn+ complex, respectively, when a potential of 0.5 V was applied.     

Photoinduced charge separation in three-layer supramolecular nanohybrids: fullerene-porphyrin-SWCNT

Photoinduced charge separation processes of three-layer supramolecular hybrids, fullerene-porphyrin-SWCNT, which are constructed from semiconducting (7,6)- and (6,5)-enriched SWCNTs and self-assembled via π-π interacting long alkyl chain substituted porphyrins (tetrakis(4-dodecyloxyphenyl)porphyrins; abbreviated as MP(alkyl)(4)) (M = Zn and H(2)), to which imidazole functionalized fullerene[60] (C(60)Im) is coordinated, have been investigated in organic solvents. The intermolecular alkyl-π and π-π interactions between the MP(alkyl)(4) and SWCNTs, in addition, coordination between C(60)Im and Zn ion in the porphyrin cavity are visualized using DFT calculations at the B3LYP/3-21G(*) level, predicting donor-acceptor interactions between them in the ground and excited states. The donor-acceptor nanohybrids thus formed are characterized by TEM imaging, steady-state absorption and fluorescence spectra. The time-resolved fluorescence studies of MP(alkyl)(4) in two-layered nanohybrids (MP(alkyl)(4)/SWCNT) revealed efficient quenching of the singlet excited states of MP(alkyl)(4) ((1)MP*(alkyl)(4)) with the rate constants of charge separation (k(CS)) in the range of (1-9) × 10(9) s(-1). A nanosecond transient absorption technique confirmed the electron transfer products, MP˙(+)(alkyl)(4)/SWCNT˙(-) and/or MP˙(-)(alkyl)(4)/SWCNT˙(+) for the two-layer nanohybrids. Upon further coordination of C(60)Im to ZnP, acceleration of charge separation via(1)ZnP* in C(60)Im→ZnP(alkyl)(4)/SWCNT is observed to form C(60)˙(-)Im→ZnP˙(+)(alkyl)(4)/SWCNT and C(60)˙(-)Im→ZnP(alkyl)(4)/SWCNT˙(+) charge separated states as supported by the transient absorption spectra. These characteristic absorptions decay with rate constants due to charge recombination (k(CR)) in the range of (6-10) × 10(6) s(-1), corresponding to the lifetimes of the radical ion-pairs of 100-170 ns. The electron transfer in the nanohybrids has further been utilized for light-to-electricity conversion by the construction of proof-of-concept photoelectrochemical solar cells.     

Functional single-wall carbon nanotube nanohybrids--associating SWNTs with water-soluble enzyme model systems

We succeeded in integrating single-wall carbon nanotubes (SWNTs), several water-soluble pyrene derivatives (pyrene(-)), which bear negatively charged ionic headgroups, and a series of water-soluble metalloporphyrins (MP(8+)) into functional nanohybrids through a combination of associative van der Waals and electrostatic interactions. The resulting SWNT/pyrene(-) and SWNT/pyrene(-)/MP(8+) were characterized by spectroscopic and microscopic means and were found to form stable nanohybrid structures in aqueous media. A crucial feature of our SWNT/pyrene(-) and SWNT/pyrene(-)/MP(8)(+) is that an efficient exfoliation of the initial bundles brings about isolated nanohybrid structures. When the nanohybrid systems are photoexcited with visible light, a rapid intrahybrid charge separation causes the reduction of the electron-accepting SWNT and, simultaneously, the oxidation of the electron-donating MP(8)(+). Transient absorption measurements confirm that the radical ion pairs are long-lived, with lifetimes in the microsecond range. Particularly beneficial are charge recombination dynamics that are located deep in the Marcus-inverted region. We include, for the first time, work devoted to exploring and testing FeP(8)(+) and CoP(8)(+) in donor-acceptor nanohybrids.     

Supramolecular carbon nanotube-fullerene donor-acceptor hybrids for photoinduced electron transfer

Photoinduced electron transfer in a self-assembled single-wall carbon nanotube (SWNT)-fullerene(C60) hybrid with SWNT acting as an electron donor and fullerene as an electron acceptor has been successfully demonstrated. Toward this, first, SWNTs were noncovalently functionalized using alkyl ammonium functionalized pyrene (Pyr-NH3+) to form SWNT/Pyr-NH3+ hybrids. The alkyl ammonium entity of SWNT/Pyr-NH3+ hybrids was further utilized to complex with benzo-18-crown-6 functionalized fullerene, crown-C60, via ammonium-crown ether interactions to yield SWNT/Pyr-NH3+/crown-C60 nanohybrids. The nanohybrids were isolated and characterized by TEM, UV-visible-near IR, and electrochemical methods. Free-energy calculations suggested possibility of electron transfer from the carbon nanotube to the singlet excited fullerene in the SWNT/Pyr-NH3+/crown-C60 nanohybrids. Accordingly, steady-state and time-resolved fluorescence studies revealed efficient quenching of the singlet excited-state of C60 in the nanohybrids. Further studies involving nanosecond transient absorption studies confirmed electron transfer to be the quenching mechanism, in which the electron-transfer product, fullerene anion radical, was possible to spectrally characterize. The rates of charge separation, kCS, and charge recombination, kCR, were found to be 3.46 x 10(9) and 1.04 x 10(7) s-1, respectively. The calculated lifetime of the radical ion-pair was found to be over 100 ns, suggesting charge stabilization in the novel supramolecular nanohybrids. The present nanohybrids were further utilized to reduce hexyl-viologen dication (HV2+) and a sacrificial electron donor, 1-benzyl-1,4-dihydronicotinamide, in an electron-pooling experiment, offering additional proof for the occurrence of photoinduced charge-separation and potential utilization of these materials in light-energy harvesting applications.     

Formation and characterization of the hexanuclear platinum cluster [Pt6(mu-PBu(t)2)4(CO)6](CF3SO3)2 through structural, electrochemical, and computational analyses

The reaction between equimolar amounts of Pt(3)(mu-PBu(t)()(2))(3)(H)(CO)(2), Pt(3)()H, and CF(3)SO(3)H under CO atmosphere affords the triangular species [Pt(3)(mu-PBu(t)()(2))(3)(CO)(3)]X, [Pt(3)()(CO)(3)()(+)()]X (X = CF(3)SO(3)(-)), characterized by X-ray crystallography, or in an excess of acid, [Pt(6)(mu-PBu(t)()(2))(4)(CO)(6)]X(2), [Pt(6)()(2+)()]X(2)(). Structural determination shows the latter to be a rare hexanuclear cluster with a Pt(4) tetrahedral core formed by joining the unbridged sides of two orthogonal Pt(3) triangles. The dication Pt(6)()(2+)() features also extensive redox properties as it undergoes two reversible one-electron reductions to the congeners [Pt(6)(mu-PBu(t)()(2))(4)(CO)(6)](+) (Pt(6)()(+)(), E(1/2) = -0.27 V) and Pt(6)(mu-PBu(t)()(2))(4)(CO)(6) (Pt(6)(), E(1/2) = -0.54 V) and a further quasi-reversible two-electron reduction to the unstable dianion Pt(6)()(2)()(-)() (E(1/2) = -1.72 V). The stable radical (Pt(6)()(+)()) and diamagnetic (Pt(6)()) species are also formed via chemical methods by using 1 or 2 equiv of Cp(2)Co, respectively; further reduction of Pt(6)()(2+)() causes fast decomposition. The chloride derivatives [Pt(6)(mu-PBu(t)()(2))(4)(CO)(5)Cl]X, (Pt(6)()Cl(+)())X, and Pt(6)(mu-PBu(t)()(2))(4)(CO)(4)Cl(2), Pt(6)()Cl(2)(), observed as side-products in some electrochemical experiments, were prepared independently. The reaction leading to Pt(3)()(CO)(3)()(+)() has been analyzed with DFT methods, and identification of key intermediates allows outlining the reaction mechanism. Moreover, calculations for the whole series Pt(6)()(2+)() --> Pt(6)()(2)()(-)()( )()afford the otherwise unknown structures of the reduced derivatives. While the primary geometry is maintained by increasing electron population, the system undergoes progressive and concerted out-of-plane rotation of the four phosphido bridges (from D(2)(d)() to D(2) symmetry). The bonding at the central Pt(4) tetrahedron of the hexanuclear clusters (an example of 4c-2e(-) inorganic tetrahedral aromaticity in Pt(6)()(2+)()) is explained in simple MO terms.     

Stability and three-dimensional aromaticity of closo-NB(n-1)H n azaboranes,n = 5-12

Computations on all the possible positional isomers of the closo-azaboranes NB(n)()(-)(1)H(n)() (n = 5-12) reveal substantial differences in the relative energies. Data at the B3LYP/6-311+G level of density functional theory (DFT) agree well with expectations based on the topological charge stabilization, with the qualitative connectivity preferences of Williams, and with the Jemmis-Schleyer six interstitial electron rules. The energetic relationship involving each of the most stable positional isomers, 1-NB(4)H(5), NB(5)H(6), 2-NB(6)H(7), 1-NB(7)H(8), 4-NB(8)H(9), 1-NB(9)H(10), 2-NB(10)H(11), NB(11)H(12), was based on the energies (DeltaH) of the model reaction: NBH(2) + (n-1)BH(increment) --> NB(n)()H(n)()(+1) (n = 4-11). This evaluation shows that the stabilities of closo-azaboranes NB(n)()(-)(1)H(n)() (n = 5-12) increase with increasing cluster size from 5 to 12 vertexes. The "three-dimensional aromaticity" of these closo-azaboranes NB(n)()(-)(1)H(n)() (n = 5-12) is demonstrated by their the nucleus-independent chemical shifts (NICS) and their magnetic susceptibilities (chi), which match one another well. However, there is no direct relationship between these magnetic properties and the relative stabilities of the positional isomers of each cluster. As expected, other energy contributions such as topological charge stabilization and connectivity can be equally important.     

Phthalocyanine-pyrene conjugates: a powerful approach toward carbon nanotube solar cells

In the present work, a new family of pyrene (Py)-substituted phthalocyanines (Pcs), i.e., ZnPc-Py and H(2)Pc-Py, were designed, synthesized, and probed in light of their spectroscopic properties as well as their interactions with single-wall carbon nanotubes (SWNTs). The pyrene units provide the means for non-covalent functionalization of SWNTs via π-π interactions. Such a versatile approach ensures that the electronic properties of SWNTs are not impacted by the chemical modification of the carbon skeleton. The characterization of ZnPc-Py/SWNT and H(2)Pc-Py/SWNT has been performed in suspension and in thin films by means of different spectroscopic and photoelectrochemical techniques. Transient absorption experiments reveal photoinduced electron transfer between the photoactive components. ZnPc-Py/SWNT and H(2)Pc-Py/SWNT have been integrated into photoactive electrodes, revealing stable and reproducible photocurrents with monochromatic internal photoconversion efficiency values for H(2)Pc-Py/SWNT as large as 15 and 23% without and with an applied bias of +0.1 V.     

Construction and photophysics study of supramolecular complexes composed of three-point binding fullerene-trispyridylporphyrin dyads and zinc porphyrin

A series of novel supramolecular complexes composed of a three-point binding C(60)-trispyridylporphyrin dyad (1) or C(70)-trispyridylporphyrin dyad (2) and zinc tetraphenylporphyrin (ZnP) were constructed by adopting a "covalent-coordinate" bonding approach, composed of three-point binding. The dyads and self-assembled supramolecular triads or pentads formed by coordinating the pyridine groups located on the dyads to ZnP, have been characterized by means of spectral and electrochemical techniques. The formation constants of ZnP-1 and ZnP-2 complexes were calculated as 1.4 × 10(4) M(-1) and 2.0 × 10(4) M(-1), respectively, and the Stern-Volmer quenching constants K(SV) were founded to be 2.9 × 10(4) M(-1) and 5.5 × 10(4) M(-1), respectively, which are much higher than those of other supramolecular complexes such as previously reported ZnP-3 (N-ethyl-2-(4-pyridyl)-3,4-fulleropyrrolidine). The electrochemical investigations of these complexes suggest weak interactions between the constituents in the ground state. The excited states of the complexes were further monitored by time-resolved fluorescence measurements. The results revealed that the presence of the multiple binding point dyads (1 or 2) slightly accelerated the fluorescence decay of ZnP in o-DCB relative to that of the "single-point" bound supramolecular complex ZnP-3. In comparison with 1 and 2, C(70) is suggested as a better electron acceptor relative to C(60). DFT calculations on a model of supramolecular complex ZnP-1 (with one ZnP entity) were performed. The results revealed that the lowest unoccupied molecular orbital (LUMO) is mainly located on the fullerene cage, while the highest occupied molecular orbital (HOMO) is mainly located on the ZnP macrocycle ring, predicting the formation of radical ion pair ZnP(+)˙-H(2)P-C(60)(-)˙ during photo-induced reaction.     

Diameter dependent electron transfer in supramolecular nanohybrids of (6,5)- or (7,6)-enriched semiconducting SWCNT as donors and fullerene as acceptor

Diameter dependent electron donor behavior of (6,5)- and (7,6)-enriched semiconducting SWCNT is proved by constructing supramolecular nanohybrids with pyrene functionalized electron acceptor, fullerene, and the subsequent photocatalytic/ photoelectrochemical processes.     

Synthesis of Polysiloxane-Bound (Ether-phosphine)palladium Complexes. Stoichiometric and Catalytic Reactions in Interphases(1)

The reaction of two equiv of the monomeric ether-phosphine O,P ligand (MeO)(3)Si(CH(2))(3)(Ph)PCH(2)-Do [1a(T(0)()), 1b(T(0)())] {Do = CH(2)OCH(3) [1a(T(0)())], CHCH(2)CH(2)CH(2)O [1b(T(0)())]} with PdCl(2)(COD) yields the monomeric palladium(II) complexes Cl(2)Pd(P approximately O)(2) [2a(T(0)())(2)(), 2b(T(0)())(2)()]. The compounds 2a(T(0)())(2)() and 2b(T(0)())(2)() are sol-gel processed with variable amounts (y) of Si(OEt)(4) (Q(0)()) to give the polysiloxane-bound complexes 2a(T(n)())(2)()(Q(k)())(y)(), 2b(T(n)())(2)()(Q(k)())(y)() (Table 1) {P approximately O = eta(1)-P-coordinated ether-phosphine ligand; for T(n)() and Q(k)(), y = number of condensed T type (three oxygen neighbors), Q type (four oxygen neighbors) silicon atoms; n and k = number of Si-O-Si bonds; n = 0-3; k = 0-4; 2a(T(n)())(2)()(Q(k)())(y)(), 2b(T(n)())(2)()(Q(k)())(y)() = {[M]-SiO(n)()(/2)(OX)(3)(-)(n)()}(2)[SiO(k)()(/2)(OX)(4)(-)(k)()](y)(), [M] = (Cl(2)Pd)(1/2)(Ph)P(CH(2)Do)(CH(2))(3)-, X = H, Me, Et}. The complexes 2b(T(n)())(2)()(Q(k)())(y)() (y = 4, 12, 36) show high activity and selectivity in the hydrogenation of 1-hexyne and tolan. The dicationic complexes [Pd(P&arcraise;O)(2)][SbF(6)](2) [3a(T(0)())(2)(), 3b(T(0)())(2)()] are formed by reacting Cl(2)Pd(P approximately O)(2) with 2 equiv of a silver salt {P&arcraise;O = eta(2)-O&arcraise;P-coordinated ether-phosphine ligand; 3a(T(0)())(2)(), 3b(T(0)())(2)() = [M]-SiOMe(3); [M] = {[Pd(2+)](1/)(2)P(Ph)(CH(2)CH(2)OCH(3))(CH(2))(3)-}{SbF(6)} (a), {[Pd(2+)](1/)(2)P(Ph)(CH(2)CHCH(2)CH(2)CH(2)O)(CH(2))(3)-}{SbF(6)} (b)}. Their polysiloxane-bound congeners 3a(T(n)())(2)(), 3b(T(n)())(2)() {[M]-SiO(n)()(/2)(OX)(3)(-)(n)} are obtained if a volatile, reversible bound ligand like acetonitrile is employed during the sol-gel process. The bis(chelate)palladium(II) complexes 3a(T(n)())(2)(), 3b(T(n)())(2)() are catalytic active in the solvent-free CO-ethene copolymerization, producing polyketones with chain lengths comparable to those obtained with chelating diphosphine ligands. The polysiloxane-bound palladium(0) complexes 5a(T(n)())(2)()(Q(k)())(4)(), 5b(T(n)())(2)()(Q(k)())(4)() {[M]-SiO(n)()(/)(2)(OX)(3)(-)(n)}(2)[SiO(k)()(/2)(OX)(4)(-)(k)](4), [M] = [(dba)Pd](1/)(2)P(Ph)(CH(2)Do)(CH(2))(3)-} undergo an oxidative addition reaction with iodobenzene in an interphase with formation of the complexes PhPd(I)(P approximately O)(2).4SiO(2) [6a(T(n)())(2)()(Q(k)())(4)(), 6b(T(n)())(2)()(Q(k)())(4)()] {[M]-SiO(n)()(/)(2)(OX)(3)(-)(n)](2)[SiO(k)()(/2)(OX)(4)(-)(k)](4), [M] = [PhPd(I)](1/2)P(Ph)(CH(2)Do)(CH(2))(3)-}, which insert carbon monoxide into the palladium-aryl bond even in the solid state.     

Self-Assembly of Ribbons and Frameworks Containing Large Channels Based upon Methylene-Bridged Dithio-, Diseleno-, and Ditelluroethers

Homoleptic copper(I) and silver(I) complexes [M(n)(L-L)(2)(n)()](BF(4))(n)() (M = Cu or Ag; L-L = MeECH(2)EMe; E = S, Se or Te) have been prepared and characterized by analysis, FAB mass spectrometry, and IR and multinuclear NMR spectroscopy ((1)H, (77)Se, (125)Te, (63)Cu and (109)Ag). The single-crystal X-ray structures of [Cu(n)()(MeSeCH(2)SeMe)(2)(n)()](PF(6))(n)() (orthorhombic, P2(1)2(1)2(1), a = 10.879(7) ?, b = 16.073(7) ?, c = 9.19(1) ?, Z = 4) and [Ag(n)()(MeSeCH(2)SeMe)(2)(n)()](BF(4))(n)() (monoclinic, P2(1)/c, a = 14.546(9) ?, b = 14.65(1) ?, c = 30.203(9) ?, Z = 4) reveal extended three-dimensional cationic frameworks in the solid state which contain large cylindrical or rectangular channels accommodating the PF(6)(-) or BF(4)(-) counterions. In contrast, a single-crystal X-ray structure of [Cu(n)()(MeSCH(2)SMe)(2)(n)()](PF(6))(n)().nMeNO(2) (orthorhombic, Pbcn, a = 15.506(3) ?, b = 8.934(2) ?, c = 25.859(3) ?, Z = 8) shows tetrahedral Cu(I) ions coordinated to bridging dithioethers forming an cationic ribbon-like arrangement of 8-membered rings. Adjacent rings are linked by the Cu atoms. Variable temperature NMR studies have been used to probe various exchange processes occurring in solution in these systems.     

Distorted fused porphyrin-phthalocyanine conjugates: synthesis and photophysics of supramolecular assembled systems with a pyridylfullerene

In the current work, we report on the synthesis and photophysical features of supramolecular hybrid systems that are based on newly fused porphyrin-phthalocyanine (P-Pc) conjugates and a pyridylfullerene. The ZnP-ZnPc conjugate was synthesized in three steps starting with a Diels-Alder reaction between β-vinylporphyrin and fumaronitrile. The resulting mixture of isomeric adducts was then dehydrogenated to yield the corresponding benzo[b]porphyrin-2(1),2(2)-dicarbonitrile. In the final step, cyclotetramerization with 4-tert-butylphthalonitrile, in the presence of zinc acetate, afforded the bis-metalated conjugate. Selective demetallation of ZnP led to the H(2)P-ZnPc conjugate. For both conjugates steric hindrance is the inception to a bent configuration, which does, however, not preclude enlargement of the π-conjugated system, that is, the porphyrins and the phthalocyanines. The two conjugates coordinate N-(4-pyridyl)fullero[c]pyrrolidine giving rise to the corresponding supramolecular porphyrin-phthalocyanine-fullerene systems. Photophysical measurements corroborate a sequential deactivation in the excited state, namely an initial intramolecular energy transfer from ZnP or H(2)P to ZnPc followed by an intramolecular charge transfer to yield ZnP-(ZnPc)˙(+)-(C(60))˙(-) and H(2)P-(ZnPc)˙(+)-(C(60))˙(-), respectively.     

Anisotropic Exchange Effects in Temperature and Pressure Dependences of EPR Zero-Field Splitting in [(C(6)H(5))(3)(n-propyl)P](2)Cu(2)Cl(6)

X-band single-crystal and powder EPR data were collected in the temperature range 4.2-300 K and under hydrostatic pressure up to 500 MPa for [(C(6)H(5))(3)(n-propyl)P](2)Cu(2)Cl(6) (C(42)H(44)P(2)Cu(2)Cl(6)). The crystal and molecular structure have been determined from X-ray diffraction. The compound crystallizes in the monoclinic space group P2(1)/n (Z = 2) and have unit cell dimensions of a = 9.556(5) ?, b= 17.113(3) ?, c = 13.523(7) ?, and beta = 96.10(4) degrees. The structure consists of two controsymmetric Cu(2)Cl(6)(2)(-) dimers well separated by complex anions. EPR spectra are typical for the triplet S = 1 state of Cu(2)Cl(6)(2)(-) dimer with parameters g(x)() = 2.114(8), g(y)() = 2.095(8), g(z)() = 2.300(8), and D(x)() = 0.025(1) cm(-)(1), D(y)() = 0.057(1) cm(-)(1), and D(z)() = -0.082(1) cm(-)(1) at room temperature. The D tensor is dominated by a contribution from anisotropic exchange but the dipole-dipole Cu-Cu coupling is not much less. The anisotropic exchange integrals were estimated to be as follows: J(xy,x)()()2(-)(y)()()2(an) = -45 cm(-)(1), J(xy,xy)()(an) = +17 cm(-)(1), J(xy,yz)()(an) = +62 cm(-)(1). The D tensor components are strongly temperature dependent and linearly increase on cooling with an anomalous nonlinear behavior below 100 K. The D values increase linearly with pressure, but the effect is much smaller than the temperature effect. This suggests that the D vs T dependence is dynamical in origin. EPR data, a possible mechanism, and contributions to the observed dependences are discussed and compared to EPR results for similar compounds.     

Non-covalent versus covalent donor-acceptor systems based on near-infrared absorbing azulenocyanines and C60 fullerene derivatives

A novel supramolecular electron donor-acceptor hybrid (2·1) and an electron donor-acceptor conjugate (3), both exhibiting a remarkably shifted Q band in the NIR region of the solar spectrum, were prepared. Irradiation of the supramolecular ensemble 2·1 within the visible range leads to a nanosecond lived radical-ion pair state Zn-azulenocyanine˙(+)-C(60)˙(-).     

Do penta- and decaphospha analogues of lithocene anion and beryllocene exist? Analysis of stability,structure, and bonding by hybrid density functional study

Stability in penta- and decaphospha analogues of lithocene anion and beryllocene is investigated by complete structural optimization at the B3LYP/6-31G level. Natural bond orbital analysis is carried out to examine the bonding between the metal and the ligands. The heterolytic dissociation energies of 667 and 608 kcal/mol predicted by B3LYP/6-311+G//B3LYP/6-31G calculations for CpBeP(5) and (P(5))(2)Be are comparable with the observed value of 635 +/- 15 kcal/mol in ferrocene. The high stability in CpBeP(5) and (P(5))(2)Be shows that these species are isolable under appropriate conditions. Lithocene anion and its phospha analogues possess lower stability toward dissociation into ionic fragments. A novel observation of the present study is that CpBeP(5) and (P(5))(2)Be have lowest energies when the two planar ligands are arranged perpendicular to each other such that one of the ligands, cyclo-P(5), is eta(1)-coordinated while the second ligand is eta(5)-coordinated to Be. The resulting structure having C(s)() point group (denoted as C(s)()(p)) is predicted to be 22 and 28 kcal/mol lower than the staggered sandwich geometry in CpBeP(5) and (P(5))(2)Be, respectively, at the B3LYP/6-311+G//B3LYP/6-31G level. In the analogous lithocene anions [CpLiP(5)](-) and [(P(5))(2)Li](-) also the C(s)()(p) structures are found to be the lowest energy structures, though their relative stabilities are small. We also characterized the geometry with both ligands eta(1)-coordinated to the metal in a linear arrangement having the D(2)(h)() point group in the decaphospha analogues [(P(5))(2)Li](-) and (P(5))(2)Be. This structure is found to be higher in energy than the C(s)()(p) structure. The D(2)(h)() structure could not be located as a potential minimum in the biscyclopentadienyl complexes and their pentaphospha analogues. Both the C(s)()(p) and D(2)(h)() structures are characterized for the first time in metallocenes. The D(2)(h)() structure seems to be a unique feature in the decaphospha metallocenes under consideration. Covalent bond formation between beryllium and phosphorus atom P(1) of eta(1)-(cyclo-P(5)) is more pronounced (bond orders 0.43-0.49) than that between Be and C(1) of eta(1)-Cp (bond orders 0.24-0.27). Though both eta(1)-coordinated cyclo-P(5) and Cp exhibit C(2)(v)() point groups, bond alternation is less pronounced in the former. The Wiberg P-P bond orders in the eta(1)-(cyclo-P(5)) of CpBeP(5) and (P(5))(2)Be having C(s)()(p) structures are in the range 1.29-1.47. These ring bond orders indicate that the P(5) ring retains aromaticity to a large extent in the eta(1)-mode of bonding with Be. Second-order perturbational energy analysis of the Fock matrix in the natural bond orbital basis reveals that there is a significant stabilizing interaction of approximately 123 kcal/mol between the lone pair orbital of P(1) and the 2s orbital of Be in the C(s)()(p) structures.     

Photoelectron imaging of hydrated carbon dioxide cluster anions

The effects of homogeneous and heterogeneous solvation on the electronic structure and photodetachment dynamics of hydrated carbon dioxide cluster anions are investigated using negative-ion photoelectron imaging spectroscopy. The experiments are conducted on mass-selected [(CO(2))(n)()(H(2)O)(m)()](-) cluster anions with n and m ranging up to 12 and 6, respectively, for selected clusters. Homogeneous solvation in (CO(2))(n)()(-) has minimal effect on the photoelectron angular distributions, despite dimer-to-monomer anion core switching. Heterogeneous hydration, on the other hand, is found to have the marked effect of decreasing the photodetachment anisotropy. For example, in the [CO(2)(H(2)O)(m)()](-) cluster anion series, the photoelectron anisotropy parameter falls to essentially zero with as few as 5-6 water molecules. The analysis of the data, supported by theoretical modeling, reveals that in the ground electronic state of the hydrated clusters the excess electron is localized on CO(2), corresponding to a (CO(2))(n)()(-).(H(2)O)(m)() configuration for all cluster anions studied. The diminishing anisotropy in the photoelectron images of hydrated cluster anions is proposed to be attributable to photoinduced charge transfer to solvent, creating transient (CO(2))(n)().(H(2)O)(m)()(-) states that subsequently decay via autodetachment.     

Kemp elimination in membrane mimetic reaction media: probing catalytic properties of catanionic vesicles formed from double-tailed amphiphiles

The rate-determining deprotonation of 5-nitrobenzisoxazole (Kemp elimination) by hydroxide is efficiently catalyzed by vesicles formed from dimethyldioctadecylammonium chloride (C(18)()C(18)()(+)()). Gradual addition of sodium didecyl phosphate (C(10)()C(10)()(-)()) leads to the formation of catanionic vesicles, which were characterized by cryo-electron microscopy, and their main phase transition temperatures (DSC) and zeta-potentials. Increasing percentages of C(10)()C(10)()(-)() in the vesicular bilayers decrease the catalysis of the Kemp elimination. A detailed kinetic analysis, supported by consideration of substrate binding site polarities and counterion binding percentages, suggest that the catalytic effects of C(18)()C(18)()(+)()/C(10)()C(10)()(-)() catanionic vesicles are primarily determined by the binding of catalytically active hydroxide ions to the vesicular surface area. The formation of neutral microdomains between 10 and 30 mol % of C(10)()C(10)()(-)() in the bilayer, as revealed by DSC, is not apparent from the catalytic effects found for these vesicles. Interestingly, the catalytic effects observed for 50 mol % C(10)()C(10)()(-)() in the catanionic vesicles indicate an asymmetric distribution of C(18)()C(18)()(+)() and C(10)()C(10)()(-)() over the bilayer leaflets. The overall kinetic results illustrate the highly complex mix of factors which determines catalytic effects on reactions occurring in biological cell membranes.     

Troposelective substitutions in microsolvated systems.

The mechanism and the stereochemistry of the intracomplex "solvolysis" of the proton-bound complexes I(X)() between CH(3)(18)OH and (R)-(+)-1-aryl-ethanol (1(R)()(X)(); aryl = phenyl (X = H); pentafluorophenyl (X = F)) have been investigated in the gas phase in the 25-100 degrees C temperature range. The results point to intracomplex "solvolysis" as proceeding through the intermediacy of the relevant benzyl cation III(X)() (a pure S(N)1 mechanism). "Solvolysis" of I(H)() leads to complete racemization at T > 50 degrees C, whereas at T < 50 degrees C the reaction displays a preferential retention of configuration. Predominant retention of configuration is also observed in the intracomplex "solvolysis" of I(F)(). This picture is rationalized in terms of different intracomplex interactions between the benzylic ion III(X)() and the nucleophile/leaving group pair, which govern the timing of their reorientation within the electrostatic complex. The obtained gas-phase picture is discussed in the light of related gas-phase and solution data. It is concluded that the solvolytic reactions are mostly governed by the lifetime and the dynamics of the species involved and, if occurring in solution, by the nature of the solvent cage. Their rigid subdivision into the S(N)1 and S(N)2 mechanistic categories appears inadequate, and the use of their stereochemistry as a mechanistic probe can be highly misleading.     

Designs,Synthesis, Characterization and Direct Electrochemistry of Zinc‐Porphyrin Bearing Pyrene Noncovalent Functionalized Graphene Oxide Sheet

We have designed and synthesis a new compound of zinc‐porphyrin bearing four pyrene groups (ZnP‐t‐P(py)₄) and prepared a new hybrid materials of ZnP‐t‐P(py)₄ with graphene oxide (GO) via non‐covalent interactions. The ZnP‐t‐P(py)₄, along with four pendant pyrene entities ZnP‐t‐P(py)₄, stacking on the (GO) surface due to π‐ π interactions, has been revealed by AFM measurements. FTIR, UV‐vis absorption confirm the non‐covalent functionalization of the GO. Raman spectral measurements revealed the electronic structure of the GO to be intact upon hybrid formation. In this donor‐acceptor nanohybrid, the fluorescence of photoexcited ZnP‐t‐P(py)₄ is effectively quenched by a possible electron‐transfer process. The fluorescence and photoelectrical response measurements also showed that this hybrid may act as an efficient photoelectric conversion material for optoelectronic applications.     

Ultrafast excitation transfer and charge stabilization in a newly assembled photosynthetic antenna-reaction center mimic composed of boron dipyrrin, zinc porphyrin and fullerene

A self-assembled supramolecular triad as a model to mimic the light-induced events of the photosynthetic antenna-reaction center, that is, ultrafast excitation transfer followed by electron transfer ultimately generating a long-lived charge-separated state, has been accomplished. Boron dipyrrin (BDP), zinc porphyrin (ZnP) and fullerene (C(60)), respectively, constitute the energy donor, electron donor and electron acceptor segments of the antenna-reaction center imitation. Unlike in the previous models, the BDP entity was placed between the electron donor, ZnP and electron acceptor, C(60) entities. For the construction, benzo-18-crown-6 functionalized BDP was synthesized and subsequently reacted with 3,4-dihydroxyphenyl functionalized ZnP through the central boron atom to form the crown-BDP-ZnP dyad. Next, an alkyl ammonium functionalized fullerene was used to self-assemble the crown ether entity of the dyad via ion-dipole interactions. The newly formed supramolecular triad was fully characterized by spectroscopic, computational and electrochemical methods. Steady-state fluorescence and excitation studies revealed the occurrence of energy transfer upon selective excitation of the BDP in the dyad. Further studies involving the pump-probe technique revealed excitation transfer from the (1)BDP* to ZnP to occur in about 7 ps, much faster than that reported for other systems in this series of triads, as a consequence of shorter distance between the entities. Upon forming the supramolecular triad by self-assembling fullerene, the (1)ZnP(*) produced by direct excitation or by energy transfer mechanism resulted in an initial electron transfer to the BDP entity. The charge recombination resulted in the population of the triplet excited state of C(60), from where additional electron transfer occurred to produce C(60)(?-):crown-BDP-ZnP(?+) ion pair as the final charge-separated species. Nanosecond transient absorption studies revealed the lifetime of the charge-separated state to be ~100 μs, the longest ever reported for this type of antenna-reaction center mimics, indicating better charge stabilization as a result of the different disposition of the entities of the supramolecular triad.