A combination of mass spectrometry, collision-induced dissociation, ion mobility mass spectrometry (IM-MS), and density functional theory (DFT) has been used to study the evolution of anionic species generated by laser-desorption of the near-planar, fluorinated polycyclic aromatic hydrocarbon (PAH), C60H21F9 (s). The dominant decay process for isolated, thermally activated C60H21F9– species comprises a sequence of multiple regioselective cyclodehydrofluorination and cyclodehydrogenation reactions (eliminating HF and H2, respectively, while forming additional pentagons and/or hexagons). The DFT calculations allow us to set narrow bounds on the structures of the resulting fragment ions by fitting structural models to experimentally determined collision cross sections. These show that the transformation of the precursor anion proceeds via a series of intermediate structures characterized by increasing curvature, ultimately leading to the closed-shell fullerene cage C60– as preprogrammed by the precursor structure.

We have combined ion mobility mass spectrometry with quantum chemical calculations to investigate the gas-phase structures of multiply negatively charged oligomers of meso-tetra(4-sulfonatophenyl)metalloporphyrins comprising the divalent metal centers ZnII, CuII, and PdII. Sets of candidate structures were obtained by geometry optimizations based on calculations at both the semiempirical PM7 and density functional theory (DFT) levels. The corresponding theoretical cross sections were calculated with the projection approximation and also with the trajectory method. By comparing these collision cross sections with the respective experimental values we were able to assign oligomer structures up to the tetramer. In most cases the cross sections of the lowest energy isomers predicted by theory were found to agree with the measurements to within the experimental uncertainty (2%). Specifically, we find that for a given oligomer size the structures are independent of the metal center but depend strongly on the charge state. Oligomers in low charge states with a correspondingly larger number of sodium counterions tend to form stacked, cofacial structures reminiscent of H-aggregate motifs observed in solution. By contrast, in higher charge states, the stack opens to form coplanar structures.

Samples of highly enriched semiconducting SWCNTs with average diameters of 1.35 nm have been prepared by combining PODOF polymer wrapping with size-exclusion chromatography. The purity of the material was determined to be >99.7% from the transfer characteristics of short-channel transistors comprising densely aligned sc-SWCNTs. The transistors have a hole mobility of up to 297 cm2V–1 s–1 and an On/Off ratio as high as 2 × 108.Keywords: carbon nanotubes; chromatography; dielectrophoresis; polymer wrapping; transistor;

We have used both action and photoelectron spectroscopy to study the response of isolated PdII meso-tetra(4-sulfonatophenyl)porphyrin tetraanions ([PdTPPS]4–) to electronic excitation over the 2.22–2.98 eV photon energy range. The action spectrum obtained by recording the wavelength-dependent intensity of charged decay products closely resembles the absorption spectrum of PdTPPS in aqueous solution (which shows pronounced Q and Soret absorption bands). The two main decay channels observed are sulfonate group loss and, predominantly, electron emission. To better understand the electron emission channel, we have also acquired photoelectron spectra at multiple detachment photon energies covering the range probed in action spectroscopy. Upon both Q and Soret band excitation, we find that electrons are emitted in three characteristic kinetic energy ranges. The corresponding detachment processes are identified as (delayed) tunneling emission from both excited singlet and triplet states (each of which is accessed by/after one-photon absorption) as well as resonant two-photon detachment. The first triplet state lifetime of isolated [PdTPPS]4– is significantly longer than 10 μs, possibly on the 100 μs time scale. We estimate that more than 50% of the electron emission observed upon photoexcitation occurs by way of this triplet state.

An apparatus is presented which combines nanoelectrospray ionization for isolation of large molecular ions from solution, mass-to-charge ratio selection in gas-phase, low-energy-ion-beam deposition into a (co-condensed) inert gas matrix and UV laser-induced visible-region photoluminescence (PL) of the matrix isolated ions. Performance is tested by depositing three different types of lanthanoid diketonate cations including also a dissociation product species not directly accessible by chemical synthesis. For these strongly photoluminescent ions, accumulation of some femto- to picomoles in a neon matrix (over a time scale of tens of minutes to several hours) is sufficient to obtain well-resolved dispersed emission spectra. We have ruled out contributions to these spectra due to charge neutralization or fragmentation during deposition by also acquiring photoluminescence spectra of the same ionic species in the gas phase.

The Schiff-base (2-aminoethyl)hydroxybenzoic acid (H2L) as a proligand was prepared in situ from 3-formylsalicylic acid and ethanolamine (ETA). The mononuclear {[Y(HL)4][ETAH]·H2O} (1) and {[Dy(HL)4] [ETAH]·3MeOH·H2O} (2) and tetranuclear {[Y4(HL)2(L)4(μ3-OH)2]·4MeOH·4H2O} (3), {[Dy4(HL)2(L)4(μ3-OH)2]·5(MeOH)2·7H2O (4), and {[Dy4(HL)8(L)2]·4MeOH·2H2O}(5) rare-earth metal complexes of this ligand could be obtained as single-crystalline materials by the treatment of H2L in the presence of the metal salts [Ln(NO3)3·(H2O)m] (Ln = Y, Dy). In the solid state, the tetranuclear compounds 3 and 4 exhibit butterfly structures, whereas 5 adopts a rectangular arrangement. Electrospray ionization mass spectrometry data of the ionic compounds 1 and 2 support single-crystal X-ray analysis. The yttrium compounds 1 and 3 show fluorescence with 11.5% and 13% quantum yield, respectively, whereas the quantum yield of the dysprosium complex 4 is low. Magnetic studies on the dysprosium compounds 4 and 5 suggest the presence of weak antiferromagnetic interactions between neighboring metal centers. Compound 4 shows single-molecule-magnet behavior with two relaxation processes, one with the effective energy barrier Ueff = 84 K and the preexponential factor τ0 = 5.1 × 10–9 s.

Fourteen different “hairy-rod” conjugated polymers, 9,9-dioctylfluorene derivatives entailing 1,2,3-triazole, azomethine, ethynyle, biphenyle, stilbene, and azobenzene lateral units, are synthesized via modular conjugation and are systematically investigated with respect to their ability to selectively disperse SWCNTs. Four polymers of the azomethine type, with unprecedented selectivity toward dispersing (8,7), (7,6), and (9,5) SWCNT species, have been identified. In particular, azomethine polymers, herein applied for the first time for SWCNT dispersion, have been evidenced to be very effective in the highly selective solubilization of SWCNTs. The experimentally observed selectivity results are unambiguously supported by molecular dynamics simulations that account for the geometrical properties and deformation energy landscape of the polymer. Specifically, the calculations accurately and with high precision predict the experimentally observed selectivity for the (7,6) and (9,5) conformations.

C58 fullerene cages made by electron-impact induced fragmentation of C60 fullerenes have been assembled into several micron thick solid films by low energy cluster beam deposition onto inert substrates held at room temperature under ultrahigh vacuum. The resulting as-prepared material, RT-C58, behaves as an amorphous wide-band semiconductor. Nanoindentation was used to measure its mechanical properties revealing that RT-C58 has a higher elastic modulus E and hardness H than the reference carbon allotropes solid C60 and Highly Ordered Pyrolytic Graphite (HOPG): E(RT-C58) = 14 GPa and H(RT-C58) = 1.2 GPa. This effect can be explained by the unique intrinsic “functionalization” of C58 cages: they comprise reactive surface sites constituted by annelated pentagon rings which give rise to covalently stabilized oligomers, –C58–C58–C58, under our deposition conditions. Annealing, thick RT-C58 films up to 1100 K in ultrahigh vacuum results in HT-C58, a new material with considerably modified electronic and vibrational properties compared to the as-prepared RT-C58 film. The associated molecular transformations, including also partial cage–cage coalescence reactions, raise the overall mechanical hardness of the material: H(HT-C58) = 3.9 GPa.

We have recorded conformer-selective, gas-phase photoelectron spectra of α-lactalbumin derived multianions generated by electrospraying solutions of both the native protein and its denatured form (as prepared by breaking the sulfur–sulfur bonds by chemical reduction). Three different groups of gas-phase multianion conformers have been observed and characterized. Highly-folded and partially-unfolded structures are obtained from solutions of the native protein. Only highly-elongated conformers are observed upon electrospraying the denatured protein. Adiabatic detachment energies were determined at several negative charge states for each conformer group. In comparison to highly-elongated conformations, highly-folded structures show a steeper decrease of electron binding energy with increasing negative charge. By comparing experimental detachment energies for highly-elongated structures with the predictions of a simple electrostatic model calculation, we have determined the effective dielectric shielding constant.

Although the sequencing of protonated proteins and peptides with tandem mass spectrometry has blossomed into a powerful means of characterizing the proteome, much less effort has been directed at their deprotonated analogues, which can offer complementary sequence information. We present a unified approach to characterize the structure and intermolecular interactions present in the gas-phase pentapeptide leucine-enkephalin anion by several vibrational spectroscopy schemes as well as by ion-mobility spectrometry, all of which are analyzed with the help of quantum-chemical computations. The picture emerging from this study is that deprotonation takes place at the C terminus. In this configuration, the excess charge is stabilized by strong intramolecular hydrogen bonds to two backbone amide groups and thus provides a detailed picture of a potentially common charge accommodation motif in peptide anions.

We have studied the formation and thermal properties of thin, deuterofullerene-containing films on Au(111) under ultrahigh vacuum conditions. The films were prepared in situ by exposure of predeposited C60 layers to a flux of atomic deuterium. With increasing deuterium dose, a D + C60 → C60Dx reaction front propagates through the fullerene film toward the gold surface. Heating the resulting deuterofullerene-containing films to >600 K leads to desorption of predominantly C60 and C60Dx. Interestingly, some D2 is also evolved while a significant fraction of the carbon initially deposited is left on the surface as nondesorbable residue. This is in contrast to analogous deuterofullerene-containing films prepared on graphite, which sublime completely but do not measurably evolve D2, suggesting that the gold surface can act as a catalyst for D2 formation. To explore this further, we have systematically studied (i) the thermal properties of C60/Au(111) reference films, (ii) the reaction of C60/Au(111) films with D atoms, and (iii) the heating-induced degradation of deuterofullerene-containing films on Au(111). In particular, we have recorded temperature-resolved mass spectra of the desorbing species (sublimation maps) as well as performed ultraviolet photoionization spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, and scanning tunneling microscopy measurements of the surfaces at various stages of study. We infer that heating deuterofullerene-containing films generates mobile deuterium atoms which can recombine to form molecular deuterium either at the gold surface or on fullerene oligomers in direct contact with it.

We describe a micro-Raman setup allowing for efficient resonance Raman spectroscopy (RRS), i.e., mapping of Raman spectra as a function of tunable laser excitation wavelength. The instrument employs angle-tunable bandpass optical filters which are integrated into software-controlled Raman and laser cleanup filter devices. These automatically follow the excitation laser wavelength and combine tunability with high bandpass transmission as well as high off-band blocking of light. Whereas the spectral intervals which can be simultaneously acquired are bandpass limited to∼350 cm–1, they can be tuned across the spectrum of interest to access all characteristic Raman features. As an illustration of performance, we present Raman mapping of single-walled carbon nanotubes (SWNTs): (i) in a small volume of water–surfactant dispersion as well as (ii) after deposition onto a substrate. A significant improvement in the acquisition time (and efficiency) is demonstrated compared to previous RRS implementations. These results may help to establish (micro) Raman spectral mapping as a routine tool for characterization of SWNTs as well as other materials with a pronounced resonance Raman response in the visible-near-infrared spectral region.

Photoelectron spectra of isolated [M–BDSZ]3− (BDSZ = bisdisulizole, M = H, Li, Na, K, Cs) triply charged anions exhibit a dominant constant electron kinetic energy (KE) detachment feature, independent of detachment wavelengths over a wide UV range. Photoelectron imaging spectroscopy shows that this constant KE feature displays an angular distribution consistent with delayed rather than direct electron emission. Time-resolved pump–probe (388 nm/775 nm) two-colour photoelectron spectroscopy reveals that the constant KE feature results from two simultaneously populated excited states, which decay at different rates. The faster of the two rates is essentially the same for all the [M–BDSZ]3− species, regardless of M. The slower process is associated with lifetimes ranging from several picoseconds to tens of picoseconds. The lighter the alkali cation is, the longer the lifetime of this state. Quantum chemical calculations indicate that the two decaying states are in fact the two lowest singlet excited states of the trianions. Each of the two corresponding photoexcitations is associated with significant charge transfer. However, electron density is transferred from different ends of the roughly chain-like molecule to its aromatic center. The energy (and therefore the decay rate) of the longer-lived excited state is found to be influenced by polarization effects due to the proximal alkali cation complexed to that end of the molecule. Systematic M-dependent geometry changes, mainly due to the size of the alkali cation, lead to M-dependent shifts in transition energies. At the constant pump wavelength this leads to different amounts of vibrational energy in the respective excited state, contributing to the variations in decay rates. The current experiments and calculations confirm excited state electron tunneling detachment (ESETD) to be the mechanism responsible for the observed constant KE feature. The ESETD phenomenon may be quite common for isolated multiply charged anions, which are strong fluorophores in the condensed phase – making ESETD useful for studies of the transient response of such species after electronic excitation.

Fractionation according to ion mobility and mass-to-charge ratio has been used to select individual isomers of deprotonated DNA oligonucleotide multianions for subsequent isomer-resolved photoelectron spectroscopy (PES) in the gas phase. Isomer-resolved PE spectra have been recorded for tetranucleotides, pentanucleotides, and hexanucleotides. These were studied primarily in their highest accessible negative charge states (3–, 4–, and 5–, respectively), as provided by electrospraying from room temperature solutions. In particular, the PE spectra obtained for pentanucleotide tetraanions show evidence for two coexisting classes of gas-phase isomeric structures. We suggest that these two classes comprise: (i) species with excess electrons localized exclusively at deprotonated phosphate backbone sites and (ii) species with at least one deprotonated base (in addition to several deprotonated phosphates). By permuting the sequence of bases in various [A5–xTx]4– and [GT4]4– pentanucleotides, we have established that the second type of isomer is most likely to occur if the deprotonated base is located at the first or last position in the sequence. We have used a combination of molecular mechanics and semiempirical calculations together with a simple electrostatic model to explore the photodetachment mechanism underlying our photoelectron spectra. Comparison of predicted to measured photoelectron spectra suggests that a significant fraction of the detected electrons originates from the DNA bases (both deprotonated and neutral).

A series of oligofluorenes was synthesized and used as a SWNT selecting template to study the chain length effect on SWNTs dispersions in toluene. The octamer exhibits the same selectivity as the corresponding polymer. Nevertheless, SWNT/oligomer complexes are unstable, which allows fast exchange of the oligomer with a coating polymer.

To date synthetic methods to selectively produce specific (n, m) single-walled carbon nanotubes (SWCNTs) are not available. Therefore, post-processing of SWCNTs including solubilization and sorting by metallicity, length, diameter, chirality or (n, m) is necessary for further applications. To reach the goal of sorting SWCNTs, we have synthesized various conjugated polymers consisting of alternating 9,9-dialkyl fluorene and 1,2,3-triazole units via copper catalyzed alkyne–azide conjugation chemistry. Their ability to selectively wrap specific (n, m) SWCNTs is investigated towards HiPco SWCNT raw materials which contain more than 40 (n, m) species and are found to be comparable to fluorene based triazole free polymers, which are typically prepared via Suzuki-type polymerization. However, the herein reported triazole-linked click polymers are significantly simpler to prepare than their Suzuki-analogs. Fluorescence and UV/Vis NIR spectroscopy were employed to analyze the SWCNTs–polymer suspensions and demonstrate their selectivity for dispersing SWCNTs.

The ability of a series of strictly alternating copolymers to selectively enwrap single-walled carbon nanotubes (SWNTs) is investigated. Seven copolymers comprising either fluorene or carbazole subunits separated by naphthalene, anthracene, and anthraquinone spacers are obtained in good yields via a Suzuki cross-coupling protocol. The 1,5-linked naphthalene, anthracene, and anthraquinone units are introduced to favor a spiral conformation of the polymer backbone in order to improve its SWNT wrapping features. Particularly high yields of polymers are obtained using the naphthalene-1,5-ditriflate precursor, highlighting the potential of bifunctional aryltriflates as precursors of copolymers. All polymers disperse HiPco SWNTs in toluene. The obtained dispersions are purified by density gradient centrifugation and their compositions are analyzed by photoluminescence (PL) spectroscopy. In their dispersing ability the polymers display more or less pronounced SWNT diameter selectivity. In particular, poly(9,9-didodecylfluorene-2,7-diyl-alt-anthracene-1,5-diyl) (P2) exhibits a strong selectivity toward SWNTs having a diameter of ≥0.95 nm, including close-to-zigzag nanotubes. SWNT dispersions of P2 are further analyzed by absorbance and Raman scattering spectroscopy. The diameter selectivity is attributed to the anthracene-1,5-diyl subunit. In order to combine diameter selectivity with the preference for large chiral angles as shown by polyfluorene, the number of fluorene subunits in the polymer backbone is doubled in P7. Indeed, to some extent, the combination of both selectivities is observed in its dispersing behavior.Keywords: conjugated copolymer; diameter selectivity; photoluminescence; selective dispersing agent; single-walled carbon nanotubes; Suzuki polymerization;

Photocleavable polymers based on 9,9-dialkylfluorene backbone and o-nitrobenzylether were designed and synthesized to obtain stable (n,m) enriched suspensions of semiconducting SWNTs in toluene. Photoirradiation of the suspensions triggered the precipitation of the SWNTs and TEM images indicate close packing of SWNTs pointing at partial removal of the coating polymer.

Time-resolved two color pump/probe spectroscopy was used to unravel the dynamics of ultrafast decay occurring upon population of the first optical bright excitonic level (E11) in quasi-monodispersed, polymer-wrapped, single-walled (9,7)-carbon nanotubes (SWNTs) in toluene at room temperature. After resonant E11 excitation, transfer of population to at least one optically dark level near E11 was observed to take place within the first picosecond. In addition, phonon-assisted E11-excitation led to transients similar to those observed upon resonant E11-excitation indicating ultrafast vibrational relaxation convoluted with the temporal resolution of 60 fs.

Physico-chemical methods to sort single-walled carbon nanotubes (SWNTs) by chiral index are presently lacking but are required for in-depth experimental analysis and also for potential future applications of specific species. Here we report the unexpected selectivity of poly(N-decyl-2,7-carbazole) to almost exclusively disperse semiconducting SWNTs with differences of their chiral indices (n − m) ≥ 2 in toluene. The observed selectivity complements perfectly the dispersing features of the fluorene analogue poly(9,9-dialkyl-2,7-fluorene), which disperses semiconducting SWNTs with (n − m) ≤ 2 in toluene. The dispersed samples are further purified by density gradient centrifugation and analyzed by photoluminescence excitation spectroscopy. All-atom molecular modeling with decamer model compounds of the polymers and (10,2) and (7,6) SWNTs suggests differences in the π−π stacking interaction as origin of the selectivity. We observe energetically favored complexes between the (10,2) SWNT and the carbazole decamer and between the (7,6) SWNT and the fluorene decamer, respectively. These findings demonstrate that subtle structural changes of polymers lead to selective solvation of different families of carbon nanotubes. Furthermore, chemical screening of closely related polymers may pave the way toward simple, low-cost, and index-specific isolation of SWNTs.

We have studied the gas-phase laser-induced fluorescence of an ensemble of buffer gas-cooled Rhodamine 6G cations (R6G+) stored in a quadrupole ion trap at 90 K. The fluorescence resulting from excitation with continuous-wave 488 nm radiation was observed to disappear almost completely on a time scale of seconds, dependent in detail on the excitation laser fluence. Such decay can be explained by the accumulation of R6G+ in a dark triplet state. This in turn facilitates the first lifetime determination of the lowest triplet state of free R6G+ by direct ground-state recovery measurements. A lower bound for the half-life was found to be ∼2 s. Adding oxygen in a volume fraction of 1% to the buffer gas leads to efficient quenching of the triplet state and correspondingly to complete suppression of the fluorescence intensity decay. Different rare gases were applied as buffers for collisional cooling, but no significant changes in the fluorescence properties were found.

To date, (n, m) single-walled carbon nanotubes (SWNTs) cannot be selectively synthesized. Therefore, postprocessing of SWNTs including solubilization and sorting is necessary for further applications. Toward this goal, we have synthesized a polymer library consisting of fluorene- and carbazole-based homo- and copolymers. Variations of the connection of these aromatics together with the incorporation of further conjugated monomers give access to a broad diversity of polymers. Their ability to selectively wrap specific (n, m) species is investigated toward HiPco SWNTs raw material which contains more than 40 (n, m) species. Absorption and fluorescence spectroscopies were used to analyze SWNTs/polymer suspensions. These results provide evidence for selective SWNTs/polymer interactions and allow a more detailed assessment of polymer structure–property relationships, thus paving the way toward custom synthesis of polymers for single (n, m) SWNTs extraction.

Photocleavable polymers based on 9,9-dialkylfluorene backbone and o-nitrobenzylether were designed and synthesized to obtain stable (n,m) enriched suspensions of semiconducting SWNTs in toluene. Photoirradiation of the suspensions triggered the precipitation of the SWNTs and TEM images indicate close packing of SWNTs pointing at partial removal of the coating polymer.

A series of oligofluorenes was synthesized and used as a SWNT selecting template to study the chain length effect on SWNTs dispersions in toluene. The octamer exhibits the same selectivity as the corresponding polymer. Nevertheless, SWNT/oligomer complexes are unstable, which allows fast exchange of the oligomer with a coating polymer.

Photoelectron spectra of isolated [M–BDSZ]3− (BDSZ = bisdisulizole, M = H, Li, Na, K, Cs) triply charged anions exhibit a dominant constant electron kinetic energy (KE) detachment feature, independent of detachment wavelengths over a wide UV range. Photoelectron imaging spectroscopy shows that this constant KE feature displays an angular distribution consistent with delayed rather than direct electron emission. Time-resolved pump–probe (388 nm/775 nm) two-colour photoelectron spectroscopy reveals that the constant KE feature results from two simultaneously populated excited states, which decay at different rates. The faster of the two rates is essentially the same for all the [M–BDSZ]3− species, regardless of M. The slower process is associated with lifetimes ranging from several picoseconds to tens of picoseconds. The lighter the alkali cation is, the longer the lifetime of this state. Quantum chemical calculations indicate that the two decaying states are in fact the two lowest singlet excited states of the trianions. Each of the two corresponding photoexcitations is associated with significant charge transfer. However, electron density is transferred from different ends of the roughly chain-like molecule to its aromatic center. The energy (and therefore the decay rate) of the longer-lived excited state is found to be influenced by polarization effects due to the proximal alkali cation complexed to that end of the molecule. Systematic M-dependent geometry changes, mainly due to the size of the alkali cation, lead to M-dependent shifts in transition energies. At the constant pump wavelength this leads to different amounts of vibrational energy in the respective excited state, contributing to the variations in decay rates. The current experiments and calculations confirm excited state electron tunneling detachment (ESETD) to be the mechanism responsible for the observed constant KE feature. The ESETD phenomenon may be quite common for isolated multiply charged anions, which are strong fluorophores in the condensed phase – making ESETD useful for studies of the transient response of such species after electronic excitation.