Poly-p-hydroquinone Ethers: Isoenergetic Molecular Wires with Length-Invariant Oxidation Potentials and Cation Radical Excitation Energies.

Typical poly-p-phenylene wires are characterized by strong interchromophoric electronic coupling with redox and optical properties being highly length-dependent. Herein we show that an incorporation of a pair of para-methoxy groups at each p-phenylene unit in poly-p-phenylene wires (i.e., PHEn) changes the nodal structure of HOMO that leads to length-invariant oxidation potentials and cation radical excitation energies. As such, PHEn represents a unique class of isoenergetic wires where hole delocalization mainly occurs via dynamic hopping and thus may serve as an efficient medium for long-range charge transfer. Availability of these wires will allow demonstration of long-range electron transfer via incoherent hopping using donor-bridge-acceptor systems with isoenergetic PHEn-based wires as bridges.

Direct observation of electron-transfer-induced conformational transformation (molecular actuation) in a bichromophoric electron donor.

With the aid of laser-flash photolysis, the one-electron oxidation of conformationally mobile tetramethoxydibenzobicyclo[4.4.1]undecane (1), using photoexcited chloranil as an oxidant, allows us to show that extended 1(+•) undergoes a conformational transformation to π-stacked folded 1(+•) on a microsecond time scale (τ ≈ 1 µs), which is at least six times longer than that found for the conformationally locked model compound.

X-ray structural characterization of charge delocalization onto the three equivalent benzenoid rings in hexamethoxytriptycene cation radical.

Definitive X-ray crystallographic evidence is obtained for a single hole (or a polaron) to be uniformly distributed on the three equivalent 1,2-dimethoxybenzenoid (or veratrole) rings in the hexamethoxytriptycene cation radical. This conclusion is further supported by electrochemical analysis and by the observation of an intense near-IR transition in its electronic spectrum, as well as by comparison of the spectral and electrochemical characteristics with the model compounds containing one and two dimethoxybenzene rings.

Molecular actuator: redox-controlled clam-like motion in a bichromophoric electron donor.

The one-electron oxidation of tetramethoxydibenzobicyclo[4.4.1]undecane (4) prompts it to undergo a clam-like electromechanical actuation into a cofacially pi-stacked conformer as established by (i) electrochemical analysis, (ii) by the observation of the intense charge-resonance transition in the near IR region in its cation radical spectrum, and (iii) by X-ray crystallographic characterization of the isolated cation radical salt (4(+*) SbCl(6)(-)).

Convergent synthesis of alternating fluorene-p-xylene oligomers and delineation of the (silver) cation-induced folding.

Convergent synthetic routes for the preparation of hitherto unknown fluorene-p-xylene oligomers (containing up to 10 fluorene moieties) from readily available starting materials are described. The conformationally adaptable monomeric receptor (which is made of a pair of fluorene and one p-xylene ring, i.e., Z1) undergoes a simple C-C bond rotation in the presence of silver cations to produce a pi-prismand-like receptor which binds a single silver cation with remarkable efficiency (i.e., K approximately 15,000 M(-1)). The data on 1H NMR spectroscopic titrations with Ag+ together with the density functional theory and AM1 calculations allows us to establish that various oligomers of Z1 (i.e., Z2-Z9) also undergo ready folding into the structures that contain multiple pi-prismand-like receptor sites in the presence of silver cations. The multiple cavities in Z3-Z9 accommodate a single silver cation per cavity with efficiency similar to that of Z1.

Preparation of a polymer-supported fluorene-based receptor for quantitative and efficient binding of silver cations.

We have designed and synthesized a polymer-supported material in which a versatile fluorene-p-xylene-based receptor is woven onto the backbone of polystyrene. This polymer-supported receptor adopts a pi-prismand-like conformation through a simple C--C bond rotation that results in the quantitative binding of a single silver cation per receptor site with a remarkable efficiency that exceeds the binding abilities of the well-known tris[2.2.2]-p-cyclophane (or pi prismand) by at least a factor of 100. More importantly, the binding event can be readily monitored by 1H NMR spectroscopy, as well as by a more sensitive emission spectroscopic technique in which the quenching of fluorescence of the receptor moiety is quantitatively related to the binding of silver cations.

Toroidal hopping of a single hole through the circularly-arrayed naphthyl groups in hexanaphthylbenzene cation radical.

Synthesis of a dendritic (soluble) hexanaphthylbenzene derivative is described in which the six naphthyl groups are connected to the central benzene ring in a propeller-shaped arrangement. Observation of multiple oxidation waves in its cyclic voltammogram as well as an intense charge-resonance transition (extending beyond 1600 nm) in its cation radical, generated by laser-flash photolysis using photoexcited chloranil as an oxidant, suggests that a single hole is mobilized via electron transfer (or hopping) over six identical (circularly arrayed) redox centers.

Simultaneous ejection of six electrons at a constant potential by hexakis(4-ferrocenylphenyl)benzene.

A simple synthesis of a dendritic hexaferrocenyl electron donor (5) is described in which six ferrocene moieties are connected at the vertices of the propeller of the hexaphenylbenzene core. The molecular structure of 5 is confirmed by X-ray crystallography. An electrochemical analysis along with redox titrations (which are tantamount to coulometry) confirmed that it ejects six electrons at a single potential. [structure: see text]

Selective intercalation of Cs+ in the "V"-shaped cavity of a bichromophoric anion radical: Cs+ assisted pi-s-pi-delocalization of an electron.

EPR studies in tetrahydrofuran, reveal that the one electron reduction of 1-(9-methyl-9H-fluoren-9-yl)-4-methylbenzene via electron transfer from cesium metal produces an anion radical that has a large affinity for the cesium cation. The affinity of this anion radical for Cs+ is so great that it will actually "suck" the Cs+ (but not Na+ or K+) right out of the grasp of 18-crown-6, leading to a cation-assisted pi-stacked complex, where the s-orbital of the metal cation is simultaneously overlapped with the pi-clouds of the phenyl and fluorenyl moieties. At ambient temperature, proton- and cesium-electron coupling constants are rapidly (on the EPR time scale) modulated as a result of the simultaneous existence of two interconverting conformers having an averaged cesium splitting (a(Cs)) of about 1.6 G. The pi-s-pi-electronic coupling can be turned on or off via the addition or removal of cesium cations. Analogous pi-s-pi-electronic coupling is observed in the 1,4-bis(9-methyl-9H-fluoren-9-yl)benzene-cesium system.

Novel potentiometric and optical silver ion-selective sensors with subnanomolar detection limits.

Ten Ag+-selective ionophores have been characterized in terms of their potentiometric selectivities and complex formation constants in solvent polymeric membranes. The compounds with pi-coordination show much weaker interactions than those with thioether or thiocarbamate groups as the coordinating sites. Long-term studies with the best ionophores show that the lower detection limit of the best Ag+ sensors can be maintained in the subnanomolar range for at least 1 month. The best ionophores have also been characterized in fluorescent microspheres. The so far best lower detection limits of 3 x 10(-11) M (potentiometrically) and 2 x 10(-11) M Ag+ (optically) are found with bridged thiacalixarenes.

A versatile and conformationally adaptable fluorene-based receptor for efficient binding of silver cation.

We have designed and synthesized a versatile fluorene-based receptor (1) in a one-pot reaction from readily available precursors, which adapts a deltaphane- or pi-prismand-like conformer via a simple C-C bond rotation. Such a conformational adaptability of 1 allows it to bind a single silver cation with remarkable efficiency (K approximately 15 000 M-1) as monitored by 1H NMR or UV-vis spectroscopy and further confirmed by competition experiments with tris[2.2.2]paracyclophane (or pi-prismand 2) as well as a model compound 3 containing only one fluoranyl ring.