Georgios Katsukis

Low dimensional nanocarbons – chemistry and energy/electron transfer reactions

This Minireview sheds light onto the electronic communication between, on one hand, low dimensional nanocarbons – single and multiwalled 1D carbon nanotubes and 2D graphene – and, on the other hand, a variety of electroactive species en-route to novel electron donor–acceptor conjugates and hybrids in relation to their covalent and non-covalent chemistry, respectively. A common denominator to any of the highlighted conjugates/hybrids is charge transport across different scales, that is, from individual molecular conjugates/hybrids to morphologically controlled devices.

Toward combining graphene and QDs: assembling CdTe QDs to exfoliated graphite and nanographene in water.

Herein, we report for the first time on a full-fledged investigation of water-soluble CdTe quantum dots (QD) that are immobilized onto exfoliated graphite (EG) and/or nanographene (NG). Particular emphasis was placed on a top-down preparation of stable aqueous dispersions-starting from natural graphite rather than graphene oxide-while preserving the intrinsic properties of graphene. To this end, we circumvented the harsh conditions commonly employed for the pre-exfoliation (i.e., Hummers method). First, a hydrophobic-hydrophobic/π-π stacking motif was tested between EG and pyrene, to which QDs are covalently attached (QD-pyrene). Second, we employed the combination of hydrophobic-hydrophobic/π-π stacking and electrostatic interactions to build up hierarchical structures composed of NG, positively charged pyrene (pyrene(+)), and negatively charged QDs. The novel nanohybrids-QD-pyrene/EG and QD/pyrene(+)/NG-were characterized with specific emphasis on electron-transfer chemistry. In fact, both assays provide kinetic and spectroscopic evidence that support electron transfer dynamics that vary, however, between EG and NG as a reflection of the different degree of graphite exfoliation.

Electron-accepting phthalocyanine–pyrene conjugates: towards liquid phase exfoliation of graphite and photoactive nanohybrid formation with graphene

Herein, we describe the synthesis of a zinc(II) alkylsulfonylphthalocyanine–pyrene conjugate, its assembly with highly exfoliated graphite, and the investigation of the photophysical properties of the resulting nanohybrid. The presence of the pyrene unit in the conjugate is decisive in terms of non-covalently immobilizing the electron accepting phthalocyanines onto the basal plane of highly exfoliated graphite. As a matter of fact, strong interactions dominate the electronic properties of the nanohybrid in both the ground and excited states. For example, femtosecond pump probe experiments assist in corroborating an ultrafast charge separation, that is, the generation of the one-electron reduced radical anion of the phthalocyanine and one-electron oxidized graphene after irradiation at 387 nm, followed by slow charge recombination.

Control over charge transfer through molecular wires by temperature and chemical structure modifications.

A series of electron donor-acceptor arrays containing π-conjugated oligofluorenes (oFL) of variable length between a zinc porphyrin (ZnP) as electron donor and fullerene (C(60)) as electron acceptor have been prepared by following a convergent synthesis. The electronic interactions between the electroactive species were determined by cyclic voltammetry, UV-visible, fluorescence, and femto/nanosecond transient absorption spectroscopy. Our studies clearly confirm that, although the C(60) units are connected to the ZnP donor through π-conjugated oFL frameworks, no significant electronic interactions prevail in the ground state. Theoretical calculations predict that a long-range electron transfer occurs primarily due to a maximized π-conjugated pathway from the donor to the acceptor. Photoexcitation of ZnP-oFL(n)-C(60) results in transient absorption maxima at 715 and 1010 nm, which are unambiguously attributed to the photolytically generated radical ion pair state, [ZnP(•+)-oFL(n)-C(60)(•-)], with lifetimes in the microsecond time regime. Temperature-dependent photophysical experiments have shown that the charge-transfer mechanism is controllable by temperature. Both charge separation and charge recombination processes give rise to a molecular wire behavior of the oFL moiety with an attenuation factor (β) of 0.097 Å(-1). The correlation β to the connection pattern between the ZnP donor and the oFL linker revealed that even small alterations of the linker π-electron system break the homogeneous π-conjugation pattern, leading to higher values of β.

Interfacing Nanocarbons with Organic and Inorganic Semiconductors: From Nanocrystals/Quantum Dots to Extended Tetrathiafulvalenes

There is no doubt that the outstanding optical and electronic properties that low-dimensional carbon-based nanomaterials exhibit call for their implementation into optoelectronic devices. However, to harvest the enormous potential of these nanocarbons it is essential to probe them in multifunctional electron donor-acceptor systems, placing particular attention on the interactions between electron donors/electron acceptors and nanocarbons. This feature article outlines challenges and recent breakthroughs in the area of interfacing organic and inorganic semiconductors with low-dimensional nanocarbons that range from fullerenes (0D) and carbon nanotubes (1D) to graphene (2D). In the context of organic semiconductors, we focus on aromatic macrocycles and extended tetrathiafulvalenes, and CdTe nanocrystals/quantum dots represent the inorganic semiconductors. Particular emphasis is placed on designing and probing solar energy conversion nanohybrids.

Decorating polyelectrolyte wrapped SWNTs with CdTe quantum dots for solar energy conversion

We report herein on the development of a synthetic route towards SWNT/polyelectrolyte/QD nanohybrids. On one hand, negatively charged thioglycolic acid capped CdTe QDs were prepared via an aqueous solution based synthesis. On the other hand, SWNTs were coated with a positively charged polyelectrolyte. By virtue of electrostatic interactions between QDs and SWNTs, SWNT/ polyelectrolyte/QD nanohybrids were realized, whose formation was corroborated by thorough spectroscopic and microscopic investigations. Of particular relevance are changes of the QD related emission - quantum yields and lifetimes - upon their integration into the nanohybrids. The latter is indicative for electronic communication between both the photo- and redoxactive constituents, namely QDs and SWNTs, whose nature is electron transfer.