Visible and near-infrared excited-state dynamics of single-walled carbon nanotubes

Excited-state lifetimes of isolated single-walled semiconducting carbon nanotubes (SWNTs) have been measured for the first time; these excited states, observed over the 400- to 1800-nm spectral domain, possess lifetimes that range from several ps to more than 100 ps. Sub-ps to ps decay components are assigned to relaxation in SWNT bundles. Interrogation of the samples with different SWNT mean diameters further confirms the dependence of the excited-state lifetime on roll-up vector. The ratio of fast and slow decaying component contributions in the first van Hove band can be viewed as a measure of the bundle content. PACS 78.67.Ch; 78.47.+p; 61.46.+w; 73.22.-f     

Effect of solvent polarity and electrophilicity on quantum yields and solvatochromic shifts of single-walled carbon nanotube photoluminescence

In this work, we investigate the impact of the solvation environment on single-walled carbon nanotube (SWCNT) photoluminescence quantum yield and optical transition energies (E(ii)) using a highly charged aryleneethynylene polymer. This novel surfactant produces dispersions in a variety of polar solvents having a wide range of dielectric constants (methanol, dimethyl sulfoxide, aqueous dimethylformamide, and deuterium oxide). Because a common surfactant can be used while maintaining a constant SWCNT-surfactant morphology, we are able to straightforwardly evaluate the impact of the solvation environment upon SWCNT optical properties. We find that (i) the SWCNT quantum yield is strongly dependent on both the polarity and electrophilicity of the solvent and (ii) solvatochromic shifts correlate with the extent of SWCNT solvation. These findings provide a deeper understanding of the environmental dependence of SWCNT excitonic properties and underscore that the solvent provides a tool with which to modulate SWCNT electronic and optical properties.     

Synthesis of water-soluble poly(p-phenyleneethynylene) in neat water under aerobic conditions via Suzuki-Miyaura polycondensation using a diborylethyne synthon

We report the synthesis, structure, and characterization of a novel ethyne synthon, 1,2-bis(4',4',5',5'-tetramethyl[1',3',2']dioxaborolan-2'-yl)ethyne (B2C2). We demonstrate the utility of B2C2 in the Suzuki-Miyaura polycondensation reaction, synthesizing a water-soluble poly(p-phenyleneethynylene) from [2,5-diiodo-1,4-bis(3-propoxy-sulfonicacid)benzene] sodium salt in neat water under an aerobic atmosphere.     

Dynamics and transient absorption spectral signatures of the single-wall carbon nanotube electronically excited triplet state

We utilize femtosecond-to-microsecond time domain pump-probe transient absorption spectroscopy to interrogate for the first time the electronically excited triplet state of individualized single-wall carbon nanotubes (SWNTs). These studies exploit (6,5) chirality-enriched SWNT samples and poly[2,6-{1,5-bis(3-propoxysulfonic acid sodium salt)}naphthylene]ethynylene (PNES), which helically wraps the nanotube surface with periodic and constant morphology (pitch length = 10 ± 2 nm), providing a self-assembled superstructure that maintains structural homogeneity in multiple solvents. Spectroscopic interrogation of such PNES-SWNT samples in aqueous and DMSO solvents using E(22) excitation and a white-light continuum probe enables E(11) and E(22) spectral evolution to be monitored concomitantly. Such experiments not only reveal classic SWNT singlet exciton relaxation dynamics and transient absorption signatures but also demonstrate spectral evolution consistent with formation of a triplet exciton state. Transient dynamical studies evince that (6,5) SWNTs exhibit rapid S(1)→T(1) intersystem crossing (ISC) (τ(ISC) ~20 ps), a sharp T(1)→T(n) transient absorption signal (λ(max)(T(1)→T(n)) = 1150 nm; full width at half-maximum ≈ 350 cm(-1)), and a substantial T(1) excited-state lifetime (τ(es) ≈ 15 μs). Consistent with expectations for a triplet exciton state, T(1)-state spectral signatures and T(1)-state formation and decay dynamics for PNES-SWNTs in aqueous and DMSO solvents, as well as those determined for benchmark sodium cholate suspensions of (6,5) SWNTs, are similar; likewise, studies that probe the (3)[(6,5) SWNT]* state in air-saturated solutions demonstrate (3)O(2) quenching dynamics reminiscent of those determined for conjugated aromatic hydrocarbon excited triplet states.     

Iterative Arylation of Amino Acids and Aliphatic Amines via δ‐C(sp3)−H Activation: Experimental and Computational Exploration

Directed C?H functionalization has been realized as a complementary tool to the traditional approaches for a straightforward access of non‐proteinogenic amino acids; albeit such a process is restricted mostly up to the γ‐position. In the present work, we demonstrate the diverse (hetero)arylation of amino acids and analogous aliphatic amines selectively at the remote δ‐position by tuning the reactivity controlled by ligands. An organopalladium δ‐C(sp³)?H activated intermediate has been isolated and crystallographically characterized. Mechanistic investigations carried out experimentally in conjunction with computational studies shed light on the difference in the mechanistic picture depending on the substrate structure.     

Ligand‐Enabled PdII‐Catalyzed Iterative γ‐C(sp3)−H Arylation of Free Aliphatic Acid

C?H functionalization of aliphatic carboxylic acids without attaching exogenous auxiliary has been so far limited at the proximal β‐position. In this work, we demonstrate a ligand enabled palladium catalyzed first regioselective distal γ‐C(sp3)?H functionalization of aliphatic carboxylic acids without incorporating an exogenous directing group. Aryl iodides containing versatile functional groups including complex organic molecules are well tolerated with good to excellent yields during the γ‐C(sp3)?H arylation reaction. Interestingly, weak coordination of carboxylate group can be further extended for sequential hetero di‐arylation. Application of the protocol has been showcased by synthesizing substituted α‐tetralone. Mechanistic investigations have been carried out to shed light on the reaction pathway.     

Unambiguous Diagnosis of Photoinduced Charge Carrier Signatures in a Stoichiometrically Controlled Semiconducting Polymer‐Wrapped Carbon Nanotube Assembly

Single‐walled carbon nanotube (SWNT)‐based nanohybrid compositions based on (6,5) chirality‐enriched SWNTs ([(6,5) SWNTs]) and a chiral n‐type polymer (S‐PBN(b)‐Ph₄PDI) that exploits a perylenediimide (PDI)‐containing repeat unit are reported; S‐PBN(b)‐Ph₄PDI‐[(6,5) SWNT] superstructures feature a PDI electron acceptor unit positioned at 3 nm intervals along the nanotube surface, thus controlling rigorously SWNT–electron acceptor stoichiometry and organization. Potentiometric studies and redox‐titration experiments determine driving forces for photoinduced charge separation (CS) and thermal charge recombination (CR) reactions, as well as spectroscopic signatures of SWNT hole polaron and PDI radical anion (PDI^?.) states. Time‐resolved pump–probe spectroscopic studies demonstrate that S‐PBN(b)‐Ph₄PDI‐[(6,5) SWNT] electronic excitation generates PDI^?. via a photoinduced CS reaction (τ_CS≈0.4 ps, Φ_CS≈0.97). These experiments highlight the concomitant rise and decay of transient absorption spectroscopic signatures characteristic of the SWNT hole polaron and PDI^?. states. Multiwavelength global analysis of these data provide two charge‐recombination time constants (τ_CR≈31.8 and 250 ps) that likely reflect CR dynamics involving both an intimately associated SWNT hole polaron and PDI^?. charge‐separated state, and a related charge‐separated state involving PDI^?. and a hole polaron site produced via hole migration along the SWNT backbone that occurs over this timescale.     

A direct route to six and seven membered lactones via γ-C(sp3)–H activation: a simple protocol to build molecular complexity

Lactones comprise a class of valuable compounds having biological as well as industrial importance. Development of a methodology to synthesize such molecules directly from readily available materials such as aliphatic carboxylic acid is highly desirable. Herein, we have reported synthesis of δ-lactones and ε-lactones via selective γ-C(sp³)–H activation. The γ-C–H bond containing aliphatic carboxylic acids provide six or seven membered lactones depending on the olefin partner in the presence of a palladium catalyst. A mechanistic investigation suggests that C–H activation is the rate-determining step. Further transformations of the lactones have been carried out to showcase the applicability of the present strategy.

Six and seven membered lactones have been synthesized directly from readily available aliphatic acids.